CONSUMER PRODUCT PROVIDING DELAYED ASSET RELEASE

专利摘要:
the present invention relates to consumer products including compositions that include coated microcapsules, said coated microcapsules including a polymeric shell and a liquid core material encapsulated therein; and a metallic coating surrounding said microcapsules and methods related thereto.
公开号:BR112017012068B1
申请号:R112017012068-2
申请日:2015-12-16
公开日:2021-04-06
发明作者:Elaine Alice Marie Baxter；Simon Richard Biggs；Olivier Jean Cayre；Zoe Dyter；James Paul Hitchcock；Lynette Anne Makins Holland；Madhuri Jayant Khanolkar；Raul RODRIGO GOMEZ；Alison Louise Tasker；David William York
申请人:Noxell Corporation；
IPC主号:

专利说明:

[0001] [001] The present description generally relates to consumer products and methods of making a consumer product including microcapsules that contain a liquid core material. BACKGROUND
[0002] [002] Several processes for microencapsulation are known. Unfortunately, many manufactured microcapsules have disadvantages that include, but are not limited to: (1) they cannot be formulated in certain classes of products due to strict formulation limits, (2) they are highly permeable when incorporated into certain products such as those that contain high levels of surfactant, solvents, and / or water, resulting in the premature release of the asset, (3) they can only effectively encapsulate a limited amount of assets, and (4) they are so stable that they do not release the asset in use or have insufficient mechanical stability to withstand the processes necessary to incorporate them into and / or manufacture a consumer product and (5) they do not adequately deposit in the location being treated with the consumer product containing the microcapsules. Thus, there is a need for microcapsules that can improve some of these known disadvantages. SUMMARY
[0003] [003] A consumer product comprising a composition, said composition comprising: an adjunct material; and a plurality of coated microcapsules, said coated microcapsule comprising i) a microcapsule comprising a polymeric shell and a liquid core material encapsulated therein; and ii) a metallic coating surrounding said microcapsule; wherein the metallic coating comprises particles of a first metal adsorbed on said polymeric shell and a film of a second metal formed thereon; and where the metallic coating has a maximum thickness of 1000 nm.
[0004] [004] A consumer product comprising a composition, said composition comprising: from 50% to 99.9% by weight of the ethanol composition; and a plurality of coated microcapsules, said coated microcapsule comprising i) a microcapsule comprising a polymeric shell and a liquid core material encapsulated therein; and ii) a metallic coating surrounding said microcapsule; wherein the metallic coating comprises particles of a first metal adsorbed on said polymeric shell and a film of a second metal formed thereon; and wherein the metallic coating has a maximum thickness of 1000 nm; optionally, in which the coated microcapsules retain more than 50% by weight of the liquid core material when tested under the Ethanol Stability Test described herein.
[0005] [005] A method of making a composition, said method comprising: combining an adjunct material with a plurality of coated microcapsules to form a composition; wherein said coated microcapsules comprise i) a microcapsule comprising a polymeric shell and a liquid core material encapsulated therein; and ii) a metallic coating surrounding said microcapsule; wherein the metallic coating comprises particles of a first metal adsorbed on said polymeric shell and a film of a second metal formed thereon; and wherein the metallic coating has a maximum thickness of 1000 nm; wherein said composition is a component of a consumer product. BRIEF DESCRIPTION OF THE DRAWINGS
[0006] [006] Although the specification concludes with the claims, it is believed that it will be better understood from the following description taken in combination with the accompanying drawings in which:
[0007] [007] Figure 1 describes a schematic diagram illustrating a process for preparing an exemplary coated microcapsule. In the described process, the emulsion pattern (a) is converted to an uncoated microcapsule (b) comprising a polymeric shell and a liquid core material. Particles of a first metal are adsorbed onto the surface of the microcapsule (c) and a continuous film of a second metal is then applied, producing a coated microcapsule (d). Shown below the schematic diagram are corresponding optical microscopy (a), transmission electron microscopy (TEM) (b, c) and scanning electron microscopy (SEM) (d) images of a microcapsule formed by such a process.
[0008] [008] Figure 2 provides SEM and TEM images obtained at various stages of preparation of a coated microcapsule comprising a poly (methyl methacrylate) shell (PMMA), a hexadecane core and a metallic coating comprising a continuous gold film formed on a layer of platinum nanoparticles. Shown are: (a) an SEM image of the uncoated microcapsules; (b) a TEM image showing the platinum nanoparticles adsorbed on the outer surface of the microcapsules; and (c) an SEM image showing the continuous gold film.
[0009] [009] Figure 3 provides optical, SEM and TEM images obtained at various stages of preparation of a coated microcapsule, the microcapsule comprising a PEMA shell, a toluene core and a metallic coating comprising a continuous silver film formed on a layer of gold nanoparticles stabilized with borohydride. Shown are: (a) an optical image showing the uncoated microcapsules; (b) TEM images showing the gold nanoparticles stabilized with borohydride adsorbed on the surface of the microcapsules; and (c) an SEM image showing the continuous silver film. Also shown is: (d) an EDX graph indicating the silver content of the metallic film.
[0010] [0010] Figure 4 is a series of TEM images showing metallic films of varying thickness.
[0011] [0011] Figure 5 provides these data.
[0012] [0012] Figure 6 provides optical, SEM and TEM images obtained at various stages of preparation of a coated microcapsule, the microcapsule comprising a PMMA shell, a hexyl salicylate core and a metallic coating comprising a layer of platinum nanoparticles stabilized with PVP and a continuous gold film arranged therein. Shown are: (a) an optical micrograph showing the uncoated microcapsules; (b) a TEM image showing the platinum nanoparticles stabilized with PVP adsorbed on the surface of the microcapsules; and (c) an SEM image showing the gold film in the microcapsules.
[0013] [0013] Figure 7a is a graph showing the performance of coated PMMA microcapsules (data points indicated as squares) and uncoated PMMA microcapsules (data points indicated as diamonds) under the Ethanol Stability Test described here. Also provided is a data point obtained after fracturing the coated PMMA microcapsules at the end of the experiment (see the data point indicated as a triangle).
[0014] [0014] Figure 7b is an SEM image showing the fractured microcapsules.
[0015] [0015] Figure 8 is a SEM image of a melamine formaldehyde wall perfume microcapsule having a full gold coating.
[0016] [0016] Figure 9 is an SEM image of a melamine formaldehyde wall perfume microcapsule having a gold coating. DETAILED DESCRIPTION
[0017] [0017] All percentages are percentages by weight based on the weight of the composition, unless otherwise specified. All reasons are reasons by weight, unless specifically stated otherwise. All numeric ranges are inclusive of narrower ranges; outlined upper and lower range limits are interchangeable to create other ranges not explicitly outlined. The number of significant digits does not convey any limitation on the quantities indicated or on the accuracy of the measurements. All measurements are understood to be made at around 25 ° C and in ambient conditions, where "ambient conditions" means conditions under about a pressure atmosphere and around 50% relative humidity.
[0018] [0018] "Adjunct material" is any material that is not a microcapsule (coated or uncoated) and which is added to the microcapsules (coated or uncoated) to form the consumer product. The adjunct material can take many forms, and it must be assessed that an adjunct material can be a pure substance or include more than one type of material such that the adjunct material is a collection / mixture of different materials, arranged in any way. Adjunct materials, however, are limited to those used in consumer products.
[0019] [0019] "Free from" means that the established ingredient has not been added to the composition. However, the established ingredient may incidentally form as a by-product or reaction product of the other components of the composition.
[0020] [0020] "Nonvolatile" refers to those materials that are liquid or solid under ambient conditions and have a measurable vapor pressure at 25 ° C. These materials typically have a vapor pressure of less than about 0.0000001 mmHg, and an average boiling point typically greater than about 250 ° C.
[0021] [0021] "Soluble" means that at least about 0.1 g of solute dissolves in 100 ml of solvent at 25 ° C and 1 atm of pressure.
[0022] [0022] "Substantially free of" means an amount of a material that is less than 1%, 0.5%, 0.25%, 0.1%, 0.05%, 0.01%, or 0.001% by weight of a composition.
[0023] [0023] "Derivatives" as used herein, include but are not limited to, amide, ether, ester, amino, carboxyl, acetyl, and / or alcohol derivatives of a given chemical.
[0024] [0024] "Skin care assets" as used here, mean substances that when applied to the skin, provide a benefit or improvement to the skin. It should be understood that skin care assets are useful not only for application to the skin, but also for hair, nails and other mammalian keratinous tissue.
[0025] [0025] "Location" means the location where the composition is applied. Non-limiting examples of a site include mammalian keratinous tissue and clothing.
[0026] [0026] "Volatile," as used here, unless otherwise specified, refers to those materials that are liquid or SOLID under ambient conditions and that have a measurable vapor pressure at 25 ° C. These materials typically have a vapor pressure greater than about 0.0000001 mmHg, alternatively from about 0.02 mmHg to about 20 mmHg, and an average boiling point typically less than about 250 ° C, alternatively less than about 235 ° C.
[0027] [0027] When the stability of the microcapsule is compromised by inclusion in a composition, a potential solution is to separate the microcapsule from the composition using a container with separate reservoirs to store incompatible ingredients. However, separating the microcapsules from the composition is not always a viable option. Consequently, the disclosed coated microcapsules can be manufactured to better control the permeability characteristics of the assets. In this respect, the coated microcapsules disclosed here are surprisingly better able to contain liquid contents without leakage over time. LIQUID CORE MATERIAL
[0028] [0028] The coated microcapsules may comprise a liquid core material encapsulated by a polymeric shell. The term "liquid core material" as used herein refers to a core material formed from one or more components, at least 90% by weight of which are liquid at standard ambient temperature and pressure. The term "standard ambient temperature and pressure" (or "STP") refers to a temperature of 25 ° C and an absolute pressure of 100 kPa. Preferably, the liquid core material comprises at least 95% by weight, for example, at least 98% by weight, of one or more components that are liquid at standard ambient temperature and pressure. In some instances, the liquid core material consists of one or more components that are liquid at standard ambient temperature and pressure. In some examples, the liquid core material includes a mixture of liquids and a solid, non-limiting examples of which include a mixture of vanillin and perfume oils.
[0029] [0029] The liquid core material may be present in the coated microcapsule in an amount of at least 1% by weight of the microcapsule, preferably in an amount of at least 30% by weight, and more preferably in an amount of at least 60% in weight. In some examples, the liquid core material is present in the coated microcapsule in an amount of 10 to 99.9% by weight of the coated microcapsule, alternatively from 40 to 90% by weight of the coated microcapsule, alternatively from 50 to 90% by weight , alternatively from 60 to 80% by weight.
[0030] [0030] In some examples, the liquid core material comprises one or more components that are volatile. Unless otherwise specified, the term "volatile" as used here refers to those materials that are liquid or solid under ambient conditions and that have a measurable vapor pressure at 25 ° C. These materials typically have a vapor pressure greater than about 0.0000001 mm Hg, for example, from about 0.02 mm Hg to about 20 mm Hg, and an average boiling point typically less than about 250 ° C, for example, less than about 235 ° C.
[0031] [0031] The liquid core material can consist of a single material or it can be formed from a mixture of different materials. In some instances, the liquid core material comprises one or more active ingredients. The coated microcapsules described here are useful with a wide variety of active ingredients (i.e. "core materials") including, by way of illustration and without limitation, perfumes; rinse aid; insect repellents; silicones; waxes; flavors; vitamins; fabric softening agents; depilatories; skin care agents; enzymes; probiotics; dye and polymer conjugate; dye and clay conjugate; perfume delivery system; sensates, in one respect a cooling agent; attractive, in one respect a pheromone; antibacterial agents; dyes; pigments; bleaches; flavoring; sweeteners; waxes; pharmaceutical products; fertilizers; herbicides and mixtures thereof. Microcapsule core materials can include materials that alter the rheology or flow characteristics, or prolong the shelf life or stability of the product. Essential oils as core materials may include, for example, illustration oil of wintergreen, cinnamon oil, clove oil, lemon oil, lime oil, orange oil, peppermint oil pepper and the like. Dyes can include fluorans, lactones, indolyl red, I6B, leuco dyes, all by way of illustration and not limitation. Particularly useful encapsulated materials are volatile fragrances.
[0032] [0032] The liquid core material preferably comprises one or more components that are soluble in oil. The use of a liquid core material that is soluble in oil will be preferable taking into account, inter alia, the production of microcapsules, which will typically be prepared by a process involving the use of an oil-in-water emulsion in which the liquid core is present in the non-aqueous phase (oil). In some instances, the liquid core material is substantially free of water. In particular, the amount of water present in the liquid core material can be less than 5% by weight, for example, less than 1% by weight, of the liquid core material. More preferably, the liquid core material consists of one or more oil-soluble components.
[0033] [0033] The liquid core material is preferably free of compounds that are capable of reacting with any of the compounds that are used to form the polymeric shell of the microcapsules. In particular, the liquid core material is preferably free of any polymerizable compounds.
[0034] [0034] In some instances, the liquid core material comprises a perfume oil formed from one or more perfume raw materials. The term "perfume oil" as used here refers to the perfume raw material, or mixture of perfume raw materials, which is used to impart an overall pleasant odor profile to the liquid core material. Thus, where different perfume raw materials are present in the liquid core material, this term refers to the overall mixture of perfume raw materials in the liquid core material. The choice of perfume raw materials defines both the intensity of odor and the character of the liquid core material. The perfume oils used in the coated microcapsules can be relatively simple in their chemical composition, for example consisting of only a single perfume raw material, or they can comprise complex mixtures of perfume raw materials, all chosen to provide a desired odor .
[0035] [0035] Perfume oil can comprise one or more perfume raw materials having a boiling point of less than 500 ° C, for example, less than 400 ° C, for example, less than 350 ° C. The boiling points of many perfume raw materials are provided in, for example, "Perfume and Flavor Chemicals (Aroma Chemicals)" by Steffen Arctander (1969) and other textbooks known in the art.
[0036] [0036] One or more perfume raw materials will typically be hydrophobic. The hydrophobicity of a given compound can be defined in terms of its partition coefficient. The term "partition coefficient" as used here refers to the ratio between the equilibrium concentration of this substance in n-octanol and in water, and is a measure of the differential solubility of said substance between these two solvents. Partition coefficients are described in more detail in U.S. 5,578,563.
[0037] [0037] The term "logP" refers to the logarithm for base 10 of the partition coefficient. LogP values can be easily calculated using a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., 30 Irvine Calif., USA or using Software Advanced Chemistry Development (ACD / Labs) 13375P 9 VI 1.02 (© 1994 - 2014 ACD / Labs).
[0038] [0038] In some examples, perfume oil comprises one or more perfume raw materials having a calculated logP (ClogP) value of about -0.5 or greater, for example greater than 0.1, per for example, greater than 0.5, for example, greater than 1.0. In some instances, perfume oil consists of one or more perfume raw materials having a ClogP value greater than 0.1, for example, greater than 0.5, for example, greater than 1.0.
[0039] [0039] In some examples, perfume oil comprises one or more perfume raw materials selected from aldehydes, esters, alcohols, ketones, ethers, alkenes, nitriles, Schiff bases, and mixtures thereof.
[0040] [0040] Examples of raw materials of aldehyde perfume include, without limitation, alpha-amylcininamaldehyde, anisic aldehyde, decyl aldehyde, lauric aldehyde, methyl n-nonyl acetaldehyde, octyl methyl acetaldehyde, nonilaldehyde, benzenocarboxaldehyde, neral, geranial , 1,1-diethoxy-3,7-dimethylocta-2,6-diene, 4-isopropylbenzaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, alpha-methyl-p-isopropyl dihydrocinamaldehyde, 3- (3- isopropylphenyl) butanal, alpha-hexylcinamaldehyde, 7-hydroxy-3,7-dimethyloctan-1-al, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, octyl aldehyde, phenylacetaldehyde, 2,4-dimethyl-3- cyclohexene-1-carboxaldehyde, hexanal, 3,7-dimethyloctanal, 6,6-dimethylbicyclo [3,1,1] hept-2-ene-2-butanal, nonanal, octanal, 2-nonenal undecenal, 2-methyl-4 - (2,6,6-trimethyl-1-cyclohexenyl-1) -2-butenal, 2,6-dimethyloctanal, 3- (Pisopropylphenyl) propionaldehyde, 3-phenyl-4-pentenalcitronelal, o / p-ethyl-alpha, alpha, 9-decennial, dimethyldihydrocinamaldehyde, p-isobutylalfamethylhydrocinamaldehyde, cis-4-decen-1-al, 2.5 -dimethyl-2-ethenyl-4-hexenal, trans-2-methyl-2-butenal, 3-methylnonanal, alpha-sinensal, 3-phenylbutanal, 2,2-dimethyl-3-phenylpropionaldehyde, m-tertbutyl-alpha- aldehyde methyldihydrocinnamic, geranyl oxyacetaldehyde, trans-4-decen-1-al, methoxycitronol, and mixtures thereof.
[0041] [0041] Examples of ester perfume raw materials include, without limitation, allyl cyclohexane-propionate, allyl heptanoate, allyl amyl glycolate, allyl caproate, amyl acetate (n-pentyl acetate), amyl propionate , benzyl acetate, benzyl propionate, benzyl salicylate, cis-3-hexenylacetate, citronellyl acetate, citronellyl propionate, cyclohexyl salicylate, dihydro isojasmonate, dimethyl benzyl carbinyl acetate, ethyl acetate, ethyl acetate acetate, butyrate ethyl, ethyl-2-methyl butrirate, ethyl-2-methyl pentanoate, phenyl acetate (1,3,3-trimethyl-2-norbornanyl acetate), tricyclodecenyl acetate, tricyclodecenyl propionate, geranyl acetate, isobutyrate cis-3-hexenyl, hexyl acetate, cis-3-hexenyl salicylate, n-hexyl salicylate, isobornyl acetate, linalyl acetate, pt-butyl cyclohexyl acetate, (-) - L-mentyl acetate, ot-butylcyclohexyl acetate, methyl benzoate, dihydro isojasmone methyl acetate, alpha-methylbenzyl acetate, methyl salicylate, 2-phenylethyl acetate, prenyl acetate, cedryl acetate, cyclabute, phenethyl phenylacetate, terpinyl formate, citronellar anthranylate, tricycle [5.2.1.0-2, 2 6] ethyl decane-2-carboxylate, n-hexyl ethyl acetoacetate, 2-tertbutyl-4-methyl cyclohexyl acetate, formic acid, 3,5,5-trimethylhexyl ester, phenethyl crotonate, cyclogeranyl acetate, crotonate geranyl, ethyl geranate, geranyl isobutyrate, 3,7-dimethyl-ethyl 2-noninoate-2,6-octadiene acid methyl ester, citronellil valerate, 2-hexenylcyclopentanone, cyclohexyl anthranylate, Lcitronyl tiglate, butyl tiglate , pentyl tiglate, geranyl caprylate, 9-decenyl acetate, 2-isopropyl-5-methylhexyl-1 butyrate, npentyl benzoate, 2-methylbutyl benzoate (and mixtures of these with pentyl benzoate), dimethyl benzyl carbinyl propionate , dimethyl benzyl carbinyl acetate, trans-2-hexen salicylate ila, dimethyl benzyl carbinyl isobutyrate, 3,7-dimethyloctyl formate, rhodinyl formate, rhodinyl isovalerate, rhodinyl acetate, rhodinyl butyrate, rhodinyl propionate, cyclohexyl ethyl acetate, neryl butyrate, tetrahydrate butyrate mircenyl, 2,5-dimethyl-2-ethylenehex-4-enoic acid, methyl ester, 2,4-dimethylcyclohexane-1-methyl acetate, ocimenyl acetate, linalyl isobutyrate, 6-methyl-5-heptenyl-1 acetate , 4-methyl-2-pentyl acetate, n-pentyl 2-methylbutyrate, propyl acetate, isopropenyl acetate, isopropyl acetate, 1-methylcycloex3-ene-carboxylic acid, methyl ester, propyl tiglate, cyclopent-3 -enyl-1-propyl / isobutyl acetate (alphavinyl), butyl 2-furoate, 2-ethyl pentenoate, (E) -methyl 3-pentenoate, 3-methoxy-3-methylbutyl acetate, n- crotonate pentyl, n-pentyl isobutyrate, propyl formate, furfuryl butyrate, methyl angelate, methyl pivalate, prenyl caproate, furfuryl propionate, diethyl malate, isopropyl 2-methylbutyrate, dimethyl malonate, bomila formate, styryl acetate, 1- (2-furyl) -1-propanone, 1-citronyl acetate, 3,7- acetate dimethyl-1,6-nonadien-3-yl, nerile crotonate, dihydromyrcenyl acetate, tetrahydromyrcenyl acetate, lavandulil acetate, 4-cyclooctenyl isobutyrate, cyclopentyl isobutyrate, 3-methyl-3-butenyl acetate, allyl acetate, geranyl formate, cis-3-hexenyl caproate, and mixtures thereof.
[0042] [0042] Examples of alcoholic perfume raw materials include, without limitation, benzyl alcohol, beta-gamma-hexenol (2-hexen-1-ol), cedrol, citronelol, cinnamic alcohol, p-cresol, chromic alcohol, dihydromyrcenol , 3,7-dimethyl-1-octanol, dimethyl benzyl carbinol, eucalyptol, eugenol, phenyl alcohol, geraniol, hydratopic alcohol, isononyl alcohol (3,5,5-trimethyl-1-hexanol), linalool, methyl cavicol (estragol) , methyl eugenol (methyl eugenyl ether), nerol, 2-octanol, oriza alcohol, phenyl hexanol (3-methyl-5-phenyl-1-pentanol), phenethyl alcohol, alpha-terpineol, tetrahydrolinalool, tetrahydromyrcenol, 4- methyl-3-decen-5-ol, 1-3,7-dimethyloctane-1-ol, 2- (furfuryl-2) -heptanol, 6,8-dimethyl-2-nonanol, ethyl norbornyl cyclohexanol, beta-methyl cyclohexane ethanol, 3,7-dimethyl- (2), 6-octen (adien) -1-ol, trans-2-undecen-1-ol, 2-ethyl-2-prenyl-3-hexenol, isobutyl benzyl carbinol, dimethyl benzyl carbinol, ocimenol, 3,7-dimethyl1,6-nonadien-3-ol (cis & trans), tetrahydromyrcenol, alpha-terpineol, 9-decene l-1,2- (2-hexenyl) -cyclopentanol, 2,6-dimethyl-2-heptanol, 3-methyl-1-octen-3-ol, 2,6-dimethyl-5-hepten-2-ol, 3,7,9-trimethyl-1,6-decadien-3-ol, 3,7-dimethyl-6-nonen-1-ol, 3,7-dimethyl-1-octin-3-ol, 2,6- dimethyl-1,5,7- octatrienol-3, dihydromyrcenol, 2,6, -trimethyl-5,9-undecadienol, 2,5-dimethyl2-propylhex-4-enol-1, (Z) -3-hexenol, o , m, p-methyl-phenylethanol, 2-methyl-5-phenyl-1-pentanol, 3-methylphenethyl alcohol, para-methyl dimethyl benzyl carbinol, methyl benzyl carbinol, p-methylphenylethanol, 3,7-dimethyl-2-octen -1-ol, 2-methyl-6-methylene-7-octen-4-ol, and mixtures thereof.
[0043] [0043] Examples of perfume ketone raw materials include, without limitation, oxacycloeptadec-10-en-2-one, benzylacetone, benzophenone, L-carvone, cis-jasmine, 4- (2,6,6-trimethyl- 3-cyclohexen-1-yl) - but-3-en-4-one, ethyl amyl ketone, alpha-ionone, beta-ionone, ethanone, octahydro-2,3,8,8-tetramethyl-2-acetonephthalene, alpha- irone, 1- (5,5-dimethyl-1-cyclohexen-1-yl) -4-penten-1-one, 3-nonanone, ethyl hexyl ketone, mentone, 4-methyl-acetophenone, gamma-methyl ionone , methyl pentyl ketone, methyl heptenone (6-methyl-5-hepten-2-one), methyl heptyl ketone, methyl hexyl ketone, delta muscenone, 2-octanone, 2-pentyl-3-methyl-2-cyclopenten-1- one, 2-heptylcyclopentanone, alpha-methionone, 3-methyl-2- (trans-2-pentenyl) -cyclopentenone, octenyl cyclopentanone, n-amylcyclopentenone, 6-hydroxy-3,7-dimethyloctanoic acid lactone, 2-hydroxy-2 -cyclohexen-1-one, 3-methyl-4-phenyl-3-buten-2-one, 2-pentyl-2,5,5-trimethylcyclopentanone, 2-cyclopentylcyclopentanol-1,5-methylhexan-2-one, range -dodecalactone, delta-dodecalactone delta-dodecalactone, gamanonalactone, delta-nonalactone, gamma-octalactone, deltaundecalactone, gamma-undecalactone, and mixtures thereof.
[0044] [0044] Examples of ether perfume raw materials include, without limitation, p-cresyl methyl ether, 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydro -cyclopenta (G) -2-benzopyran, beta-naphthyl methyl ether, methyl isobutenyl tetrahydropyran, 5-acetyl-1,1,2,3,3,6-hexamethylindane (phantom), 7-acetyl-1,1 , 3,4,4,6-hexamethyltetralin (tonalide), 2-phenylethyl-3-methylbut-2-enyl ether, geranyl ethyl ether, isopropyl phenylethyl ester, and mixtures thereof.
[0045] [0045] Examples of alkene perfume raw materials include, without limitation, allo-ocimene, camphene, beta-karyophylene, cadinene, diphenylmethane, d-limonene, limolene, beta-myrcene, para-cymene, 2-alpha-pinene , betapinene, alpha-terpinene, gamma-terpinene, terpineolene, 7-methyl-3-methylene-1,6-octadiene, and mixtures thereof.
[0046] [0046] Examples of nitrile perfume raw materials include, without limitation, 3,7-dimethyl-6-octenenitrile, 3,7-dimethyl-2 (3), 6-nonadienenitrile, (2E, 6Z) -2, 6-nonadienenitrile, n-dodecane nitrile, and mixtures thereof.
[0047] [0047] Examples of Schiff-based perfume raw materials include, without limitation, citronellil nitrile, nonanal / methyl anthranilate, methyl ester of N-octyldene anthranilic acid, hydroxycitronellal / methyl anthranilate, cyclamen aldehyde / anthranylate methyl, methoxyphenylpropanal / methyl anthranilate, ethyl p-aminobenzoate / hydroxycitroneal, citral / methyl anthranylate, 2,4-dimethylcyclohex-3-enocarbaldehyde, hydroxycitroneal-indole methyl anthranylate, and mixtures thereof.
[0048] [0048] Non-limiting examples of other perfume raw materials useful here include pro-fragrances such as acetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances, hydrolyzable inorganic-organic fragrances, and mixtures thereof. Fragrance materials can be released from pro-fragrances in several ways. For example, the fragrance can be released as a result of simple hydrolysis, or by a change in an equilibrium reaction, or by a pH mug, or by enzymatic release.
[0049] [0049] In some examples, perfume oil comprises one or more of the perfume raw materials reported in the list above. In some instances, perfume oil comprises a plurality of perfume raw materials reported in the list above.
[0050] [0050] In some examples, the liquid core material comprises one or more perfume oils of natural origin. In some instances, the liquid core material comprises one or more perfume oils selected from musk oil, civet, castoreal, ambergris, nutmeg extract, cardamom extract, ginger extract, cinnamon extract, oriza oil , geranium oil, orange oil, mandarin oil, orange flower extract, cedar wood, vetiver, lavender, ylang-ylang extract, tuberose extract, sandalwood oil, bergamot oil, rosemary oil, oil peppermint oil, peppermint oil, lemon oil, lavender oil, citronella oil, chamomile oil, clove oil, sage oil, neroli oil, labdanum oil, eucalyptus oil, verbena, mimosa extract, narcissus extract, carrot seed extract, jasmine extract, oliban extract, rose extract, and mixtures thereof. One or more of these perfume oils can be used with one or more of the perfume raw materials reported above.
[0051] [0051] Perfume oil can be present in the liquid core material in an amount of 0.1 to 100% by weight of the liquid core material. In some instances, the liquid core material essentially consists, for example, of, a perfume oil. In some examples, perfume oil is present in the liquid core material in an amount of at least 10% by weight of the liquid core material, preferably at least 20% by weight, and more preferably at least 30% by weight. In some examples, perfume oil is present in the liquid core material in an amount of 80 to 100% by weight of the liquid core material, alternatively less than 80% by weight of the liquid core material, alternatively less than 70 % by weight, alternatively less than 60% by weight. In some instances, perfume oil is present in an amount of 10 to 50% by weight of the liquid core material, more preferably 15 to 30%. Preferred liquid core materials contain from 10 to 80% by weight of a perfume oil, preferably from 20 to 70%, more preferably from 30 to 60%.
[0052] [0052] The liquid core material may comprise one or more components in addition to perfume oil. For example, the liquid core material can comprise one or more diluents. Examples of diluents include mono-, di- and tri-esters of C4-C24 fatty acids and glycerin, isopropyl myristate, soybean oil, hexadecanoic acid, methyl ester, isododecane, and mixtures thereof. Where present, diluents are preferably present in the liquid core material in an amount of at least 1% by weight of the liquid core material, for example, from 10 to 60% by weight of the liquid core material. POLYMERIC SHELL
[0053] [0053] The liquid core material is encapsulated by a polymeric shell. The coated microcapsules can be prepared by first forming the polymeric shell around the liquid core material to form an uncoated microcapsule, and subsequently forming the metallic coating. The term "uncoated microcapsule" as used herein refers to the microcapsule comprising the liquid core material prior to coating with the metallic coating.
[0054] [0054] The polymeric shell may comprise one or more polymeric materials. For example, the polymeric shell may comprise one or more polymers chosen from synthetic polymers, naturally occurring polymers, and combinations thereof. Examples of synthetic polymers include, without limitation, nylon, polyethylenes, polyamides, polystyrenes, polyisoprene, polycarbonates, polyesters, polyureas, polyurethanes, polyolefins, polysaccharides, epoxy resins, vinyl polymers, polyacrylates, and combinations thereof. Examples of synthetic polymers include, without limitation, silk, wool, gelatin, cellulose, alginate, proteins, and combinations thereof. The polymeric shell may comprise a homopolymer or a copolymer (for example, a block copolymer or a graft copolymer).
[0055] [0055] In some examples, the polymeric shell comprises a polyacrylate, for example, poly (methyl methacrylate) (PMMA) or poly (ethyl methacrylate) (PEMA). The polyacrylate can be present in an amount of at least 5%, at least 10%, at least 25%, at least 30%, at least 50%, at least 70%, or at least 90% by weight of the polymeric shell.
[0056] [0056] In some examples, the polymeric shell comprises a random polyacrylate copolymer. For example, the random polyacrylate copolymer may comprise: an amine content of 0.2 to 2.0% by weight of the total polyacrylate mass; a carboxylic acid content of 0.6 to 6.0% by weight of the total polyacrylate mass; and a combination of an amine content of 0.1 to 1.0% and a carboxylic acid content of 0.3 to 3.0% by weight of the total polyacrylate mass.
[0057] [0057] In some examples, the microcapsule shell comprises a reaction product of a first mixture in the presence of a second mixture comprising an emulsifier, the first mixture comprising a reaction product of i) a soluble or dispersible amine oil with ii) a multifunctional acrylate or methacrylate monomer or oligomer, an oil-soluble acid and an initiator, the emulsifier comprising a water-soluble or water-dispersible acrylic acid copolymer, an alkali or alkaline salt, and optionally an aqueous phase initiator . In some examples, said amine is selected from the group consisting of aminoalkyl acrylates, aminoalkyl alkyl acrylates, aminoalkyl dialkyl acrylates, aminoalkyl methacrylates, alkylamino aminoalkyl methacrylates, dialkyl aminoalkyl methacrylates, butyl methacrylates, diethyl methacrylates, butyl methacrylates, butyl methacrylates. , dimethylaminoethyl methacrylates, dipropylaminoethyl methacrylates, and mixtures thereof. In some examples, said amine is an aminoalkyl acrylate or aminoalkyl methacrylate.
[0058] [0058] In some examples, the polymeric shell comprises a reaction product of an amine with an aldehyde. For example, the polymeric shell may comprise a reaction product selected from urea crosslinked with formaldehyde or glutaraldehyde; formaldehyde crosslinked melamine; gelatin polyphosphate coacervates optionally cross-linked with gluteraldehyde; arabic gelatinagoma coacervates; cross-linked silicone fluids; polyamines reacted with polyisocyanates; acrylate monomers polymerized by free radical polymerization, and mixtures thereof. In some examples, the polymeric shell comprises a reaction product selected from urea-formaldehyde (i.e., the reaction product from urea cross-linked with formaldehyde) and melamine resin (i.e., melamine cross-linked with formaldehyde).
[0059] [0059] In some examples, the polymeric shell comprises gelatin, optionally in combination with one or more additional polymers. In some examples, the polymeric shell comprises gelatin and polyurea.
[0060] [0060] The polymeric shell may comprise one or more components in addition to the one or more wall-forming polymers. Preferably, the polymeric shell further comprises an emulsifier. In this regard, and as described in more detail below, the encapsulation of the liquid core material can be obtained by providing an oil-in-water emulsion in which the droplets of an oily (non-aqueous) phase comprising the liquid core material they are dispersed in a continuous aqueous phase, and then a polymeric shell is formed around the droplets. Such processes are typically carried out in the presence of an emulsifier (also known as a stabilizer), which stabilizes the emulsion and reduces the likelihood of microcapsule aggregation during polymeric shell formation. Emulsifiers normally stabilize the emulsion by orienting itself on the oil phase / aqueous phase interface, thus establishing a steric and / or charged boundary layer around each droplet. This layer serves as a barrier to other particles or droplets preventing their intimate contact and coalescence, thereby maintaining a uniform droplet size. Since the emulsifier will typically be retained in the polymeric shell, the polymeric shell of the microcapsules can comprise an emulsifier as an additional component. The emulsifier can be adsorbed on and / or absorbed into the polymeric shell of the microcapsules.
[0061] [0061] The emulsifier can be a polymer or a surfactant. The emulsifier can be a nonionic, cationic, anionic, zwitterionic or amphoteric emulsifier. Examples of suitable emulsifiers include, without limitation, cetyl trimethylammonium bromide (CTAB), poly (vinyl alcohol) (PVA), poly (vinyl pyrrolidone) (PVP), poly (acrylic acid) (PAA), poly (metracrylic acid) ( PMA), dodecyldimethyl ammonium bromide (DDAB), sodium dodecyl sulfate (SDS) and poly (ethylene glycol). In some examples, the emulsifier is selected from cetyl trimethylammonium bromide, poly (vinyl alcohol) and poly (vinyl pyrrolidone).
[0062] [0062] Uncoated microcapsules can be formed by emulsifying the liquid core material in droplets and forming a polymeric shell around the droplets. Microencapsulation of the liquid core material can be conducted using a variety of methods known in the art, including coacervation methods, in situ polymerization methods and interfacial polymerization methods. Such techniques are known in the art (see, for example, "Microencapsulation: Methods and Industrial Applications", Edited by Benita and Simon, Marcel Dekker, Inc., 1996; US 2,730,456; US 2,800,457; US 2,800,458; US 2,800,458; US 4,552,811; US 6,592,990; and US 2006/0263518).
[0063] [0063] In some examples, microcapsules are prepared by a coacervation method that involves oil-in-water emulsification followed by solvent extraction. Such procedures are known in the art (see, for example, Loxley et al., Journal of Colloid and Interface Science, vol. 208, pages 49 - 62, 1998) and involve the use of a non-aqueous phase comprising a polymeric material that is capable of forming a polymeric shell, a deficient solvent for the polymeric material, and a co-solvent which is a good solvent for the polymeric material. The non-aqueous and aqueous phases are emulsified, forming an oil-in-water emulsion comprising droplets of the non-aqueous phase dispersed in the continuous aqueous phase. The cosolvent is then partially or completely extracted from the non-aqueous phase, causing the polymeric material to precipitate around the deficient solvent, thereby encapsulating the deficient solvent.
[0064] [0064] Uncoated microcapsules can be prepared by: (i) providing a non-aqueous phase comprising a polymeric material that is capable of forming a polymeric shell, a liquid core material that is a deficient solvent for the polymeric material, and a co-solvent which is a good solvent for the polymeric material; (ii) providing an aqueous phase; (iii) emulsifying the non-aqueous phase and the aqueous phase to form an emulsion comprising droplets of the non-aqueous phase dispersed within the aqueous phase; and (iv) extracting at least a portion of the co-solvent from the non-aqueous phase such that the polymeric material precipitates around droplets comprising the liquid core material, thereby encapsulating the liquid core material.
[0065] [0065] In some examples, the polymeric material comprises a polyacrylate, for example, poly (methyl methacrylate) (PMMA), poly (ethyl methacrylate) (PEMA) or a combination of these. In some examples, the polymeric material consists of poly (methyl methacrylate) (PMMA) or poly (ethyl methacrylate) (PEMA).
[0066] [0066] Preferably, the polymeric material has a weighted average molecular weight of at least 10 kDa, more preferably at least 50 kDa, more preferably at least 100 kDa. Preferably, the polymeric material has a weighted average molecular weight of 10 to 1000 kDa, more preferably 50 to 800 kDa, more preferably 100 to 600 kDa.
[0067] [0067] With regard to the chemical composition of the non-aqueous phase, the liquid core material is preferably present in an amount of 0.5 to 50%, preferably 1 to 45%, and more preferably 3 to 40% by weight of the non-aqueous phase. The polymeric material is preferably present in the non-aqueous phase in an amount of 0.5 to 15%, preferably 1 to 10%, and more preferably 2 to 8% by weight of the non-aqueous phase. The cosolvent is preferably present in an amount of 40 to 98%, preferably 50 to 98%, and more preferably 60 to 95% by weight of the non-aqueous phase. In some examples, the non-aqueous phase consists of the liquid core material, the polymeric material and the co-solvent.
[0068] [0068] In some examples, the cosolvent is a volatile material, for example, dichloromethane (DCM), and is extracted from the non-aqueous phase by evaporation. In this case, the precipitation of the polymeric material can be aided by heating the emulsion to promote the evaporation of the co-solvent. For example, the method can be carried out at a temperature of at least 30 ° C.
[0069] [0069] Preferably, at least one of the aqueous and non-aqueous phases comprises an emulsifier. More preferably, the aqueous phase comprises an emulsifier. Examples of emulsifiers include, without limitation, poly (vinyl alcohol) (PVA), poly (vinyl pyrrolidone) (PVP), cetyl trimethylammonium bromide (CTAB) and mixtures thereof. In some examples, the emulsifier is present in an amount of 0.01 to 50% by weight of the aqueous phase, preferably from 0.5 to 30%, and more preferably from 0.1 to 10% by weight.
[0070] [0070] In some examples, the polymeric shell is formed by a process of interfacial polymerization. For example, the polymeric shell can be prepared by an interfacial polymerization process that involves the use of a non-aqueous phase comprising the liquid core material and one or more oil-soluble monomers; and an aqueous phase comprising one or more water-soluble monomers and an emulsifier. The non-aqueous and aqueous phases are emulsified to form an emulsion comprising droplets of the non-aqueous phase dispersed within the aqueous phase. The monomers are then polymerized, typically by heating, with polymerization occurring at the interface between the non-aqueous phase and the aqueous phase.
[0071] [0071] Alternatively, the polymeric shell may be obtainable by interfacial polymerization of a prepolymer. Such processes can be used to prepare a range of different polymeric shell materials. For example, a polymeric shell comprising a polyacrylate, polyamine or polyurea material can be prepared by such a process.
[0072] [0072] Preferably, the polymeric material comprises a polyacrylate. In some examples, the polymeric shell comprises a polyacrylate and is obtainable by interfacial polymerization of a prepolymer, in which the prepolymer is obtained by reacting a mixture comprising: (i) an aminoalkyl acrylate monomer, a methacrylate monomer aminoalkyl, or a mixture thereof; and (ii) an acrylate monomer, a methacrylate monomer, an acrylate oligomer, a methacrylate oligomer, or a mixture thereof.
[0073] (i) fornecer uma fase não aquosa compreendendo o material de núcleo líquido, um monômero de amina, um monômero ou oligômero de acrilato ou metacrilato multifuncional, um ácido e um iniciador de radical livre; (ii) reagir o monômero de amina com o monômero ou oligômero de acrilato ou metacrilato multifuncional para formar um prépolímero; (iii) fornecer uma fase aquosa compreendendo um emulsificador, um álcali ou sal alcalino, e opcionalmente um iniciador de radical livre; (iv) contatar a fase não aquosa com a fase aquosa sob condições tal que uma emulsão seja formada compreendendo gotículas da fase não aquosa dispersas na fase aquosa; e (v) polimerizar o pré-polímero para formar uma casca polimérica que encapsula as gotículas líquidas. [0073] More preferably, the polymeric shell is prepared by a process comprising: (i) providing a non-aqueous phase comprising the liquid core material, an amine monomer, a multifunctional acrylate or methacrylate monomer or oligomer, an acid and a free radical initiator; (ii) reacting the amine monomer with the multifunctional acrylate or methacrylate monomer or oligomer to form a prepolymer; (iii) providing an aqueous phase comprising an emulsifier, an alkali or alkaline salt, and optionally a free radical initiator; (iv) contacting the non-aqueous phase with the aqueous phase under conditions such that an emulsion is formed comprising droplets of the non-aqueous phase dispersed in the aqueous phase; and (v) polymerize the prepolymer to form a polymeric shell that encapsulates the liquid droplets.
[0074] [0074] The amine monomer is an oil-soluble or oil-dispersible amine monomer, more preferably an aminoalkyl acrylate or aminoalkyl methacrylate. In some examples, the amine monomer is selected from aminoalkyl acrylates, alkylalkyl acrylates, dialkyl aminoalkyl acrylates, aminoalkyl methacrylates, alkylamino aminoalkyl methacrylates, dialkyl aminoalkyl methacrylates, butylethyl methacrylates, methylacrylate, methylacrylate, methylacrylate dimethylaminoethyl, dipropylaminoethyl methacrylates, and mixtures thereof. Preferred amine monomers are diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, tert-butyl aminoethyl methacrylate, and mixtures thereof. More preferably, the amine is tert-butylaminoethyl methacrylate and the multifunctional acrylate or methacrylate monomer or oligomer is a hexafunctional aromatic urethane acrylate oligomer.
[0075] [0075] In the above process, an aqueous phase comprising an emulsifier and an alkali or alkaline salt is used. Examples of emulsifiers include, without limitation, poly (vinyl alcohol) (PVA), poly (vinyl pyrrolidone) (PVP), cetyl trimethylammonium bromide (CTAB), and mixtures thereof. In some examples, the alkali or alkaline salt is sodium hydroxide.
[0076] [0076] The interfacial polymerization process is preferably carried out in the presence of a free radical initiator. Examples of suitable free radical initiators include azo, peroxide, alkyl peroxides, dialkyl peroxides, peroxyesters, peroxycarbonates, peroxycarbonates and peroxydicarbonates. In some examples, the free radical initiator is selected from 2,2'-azobis- (2,4-dimethylpentanonitrile), 2,2'-azobis- (2-methyl-butyronitrile), and mixtures thereof. A free radical initiator can be present in the aqueous phase, in the non-aqueous phase, or both.
[0077] [0077] In some examples, microcapsules are prepared by an in situ polymerization process. Such processes are known in the art and generally involve preparing an emulsion comprising droplets of liquid core material dispersed in a continuous phase comprising a precursor material that can be polymerized to form a polymeric shell; and polymerizing the precursor material to form a polymeric shell, thereby encapsulating the liquid droplets. The polymerization process is similar to that of interfacial polymerization processes, except that no precursor material for the polymeric shell is included in the liquid core material in in situ polymerization processes. Thus, polymerization occurs only in the continuous phase, rather than anywhere on the interface between the continuous phase and the core material.
[0078] [0078] Examples of precursor materials for the polymeric shell include, without limitation, prepolymer resins such as urea resins, melamine resins, acrylate esters, and isocyanate resins. Preferably, the polymeric shell is formed by the polymerization of a precursor material selected from: melamine-formaldehyde resins; urea-formaldehyde resins; monomeric or low molecular weight polymers of methylol melamine; monomeric or low molecular weight polymers of dimethylol urea or dimethylol methyl urea; and partially methylated methylol melamine.
[0079] [0079] The use of melamine-formaldehyde resins or urea-formaldehyde resins as the precursor material is particularly preferred. Procedures for preparing microcapsules comprised of such precursor materials are known in the art (see, for example, US 3,516,941, US 5,066,419 and US 5,154,842). The capsules are manufactured first by emulsifying the liquid core material as small droplets in an aqueous phase comprising melamine-formaldehyde or urea-formaldehyde resin, and then allowing the polymerization reaction to proceed along with precipitation at the oil interface. -Water.
[0080] (i) fornecer uma fase não aquosa compreendendo o material de núcleo líquido; (ii) fornecer uma fase aquosa compreendendo um prépolímero de melamina-formaldeído (por exemplo, uma resina de metilol melamina parcialmente metilada); (iii) emulsificar as fases não aquosas e aquosas para formar uma emulsão compreendendo gotículas da fase não aquosa dispersas na fase aquosa; e (iv) condensar o pré-polímero de melamina-formaldeído, desse modo formando um polímero de melamina-formaldeído que precipita da fase aquosa e encapsula as ditas gotículas. [0080] In some examples, microcapsules can be prepared by a process comprising: (i) providing a non-aqueous phase comprising the liquid core material; (ii) providing an aqueous phase comprising a melamine-formaldehyde prepolymer (for example, a partially methylated methylol melamine resin); (iii) emulsifying the non-aqueous and aqueous phases to form an emulsion comprising droplets of the non-aqueous phase dispersed in the aqueous phase; and (iv) condensing the melamine-formaldehyde prepolymer, thereby forming a melamine-formaldehyde polymer that precipitates from the aqueous phase and encapsulates said droplets.
[0081] [0081] The polymerization process is preferably carried out using an emulsifier, which is preferably present in the aqueous phase. By way of illustration, an anionic emulsifier (for example, butyl acrylate and acrylic acid copolymers) and / or a neutral emulsifier (for example, PVP) can be used.
[0082] [0082] The condensation of the melamine-formaldehyde prepolymer can be initiated, for example, by reducing the pH of the emulsion. The pH of the emulsion can be adjusted using a base as appropriate. Examples of suitable bases include alkali metal hydroxides (for example, sodium hydroxide), ammonia, and triethanolamine.
[0083] [0083] In each of the emulsification processes described herein, emulsification can be conducted using any suitable mixing device known in the art. For example, a homogenizer, colloid mill, ultrasonic dispersion device, or ultrasonic emulsifier can be used. Preferably, a homogenizer is used.
[0084] The resulting polymeric shell may have a thickness greater than 0.5 nm, preferably greater than 1 nm, and more preferably greater than 2 nm. Typically, the polymeric shell will have a shell thickness of less than 2000 nm, preferably less than 1500 nm, and more preferably less than 1100 nm. The microcapsules preferably have a polymeric shell with a thickness of 1 to 2000 nm, such as from 2 to 1100 nm. Factors such as the concentration of the shell-forming material in the emulsion will dictate the thickness of the polymeric shell.
[0085] [0085] The size of the microcapsules can be controlled by changing factors such as the stirring speed and the shape of the stirring blade or rotating blade of the agitator or homomixer used during the emulsification step of the microencapsulation process, or adjusting to reaction rate by changing the polymerization conditions (for example, the temperature and reaction time) for the polymeric material. In particular, the size of the microcapsules can be controlled by regulating the stirring speed, which in turn regulates the size of the droplets of the liquid core material in the emulsion. METALLIC COATING
[0086] [0086] The coated microcapsules may further comprise a metallic coating that surrounds the microcapsules. The metallic coating has a maximum thickness of 1000 nm and comprises particles of a first metal adsorbed on the polymeric shell and a film of a second metal disposed on said particles. The film of the second metal provides a continuous coating that surrounds the surface of the microcapsule. Preferably the thickness of the metallic coating is substantially uniform throughout the coating.
[0087] [0087] The particles of the first metal are preferably nanoparticles. The term "nanoparticles" as used herein refers to particles having a particle size of 1 to 200 nm. Preferably, the metal nanoparticles have a particle size of less than 100 nm, for example, less than 50 nm. More preferably, the metal nanoparticles have a particle size of less than 10 nm, more preferably less than 5 nm, and more preferably less than 3 nm. In this regard, the use of smaller metal nanoparticles can result in the formation of a thinner metallic coating. Nanoparticles will typically have a spheroidal geometry, but they can exist in more complex shapes such as sticks, stars, ellipsoids, cubes or leaves.
[0088] [0088] In some examples, nanoparticles comprise nanoparticles of gold, silver, copper, tin, cobalt, tungsten, platinum, palladium, nickel, iron or aluminum, or mixtures thereof. In some examples, nanoparticles comprise an alloy of two or more metals, for example, an alloy of two or more metals selected from gold, silver, copper, tin, cobalt, tungsten, platinum, palladium, nickel, iron and aluminum. In some examples, nanoparticles comprise a metal oxide, for example, aluminum oxide or an iron oxide. In some examples, nanoparticles comprise core-shell particles comprising a core of a first metal or metal oxide surrounded by a shell of a second metal or metal oxide. In some examples, nanoparticles consist of a single metal.
[0089] [0089] As described in more detail below, the film of the second metal is preferably applied by a non-electrical deposition procedure that is catalyzed by the particles of the first metal. Therefore, it is preferred that the particles of the first metal comprise a metal that catalyzes the non-electrical deposition process.
[0090] [0090] The first metal can be selected from the transition metals and p-block metals, for example, a metal selected from those metals listed in Groups 9 to 14 of the Periodic Table, in particular a metal selected from Groups 10, 11 and 14. Preferably, the first metal is a metal selected from nickel, palladium, platinum, silver, gold, tin and combinations thereof. Preferably, the first metal comprises platinum, silver, gold, or a mixture thereof.
[0091] [0091] The first and second metals can be the same or different. Preferably, the second metal is different from the first metal.
[0092] [0092] The second metal is preferably a metal that is capable of being deposited through a non-electrical deposition process. The second metal can be a transition metal, for example, a metal selected from those metals listed in Groups 9 to 14 of the Periodic Table, in particular a metal selected from Groups 10 and 11. Preferably, the second metal is a metal selected from silver. , gold, copper and combinations of these.
[0093] [0093] In some examples, the first metal is selected from Au, Pt, Pd, Sn, Ag and combinations of these; and the second metal is selected from Au, Ag, Cu, Ni and combinations of these.
[0094] [0094] In some examples, the first metal is selected from Au, Pt, Pd, Sn, Ag and combinations of these (for example, Sn / Ag) and the second metal is Au. In some examples, the first metal is selected from Sn, Pt, Ag, Au and combinations of these (for example, Pt / Sn) and the second metal is Ag. In some examples, the first metal is selected from Sn, Ag, Ni and combinations of these (for example, Sn / Ni or Sn / Ag) and the second metal is Cu. In some examples, the first metal is selected from Sn, Pd, Ag and combinations of these (for example, Sn / Pd) and the second metal is Ni.
[0095] [0095] In some examples, the first metal is Pt and the second metal is Au; the first metal is Au and the second metal is Ag; or the first metal is Au and the second metal is Cu. Most preferably, the first metal is Au and the second metal is Ag; or the first metal is Pt and the second metal is Au.
[0096] [0096] The particles of the first metal are preferably adsorbed on the polymeric shell in the form of a discontinuous layer such that, prior to the application of the metallic film, the surface of the polymeric shell comprises regions comprising adsorbed metal particles and regions in which the adsorbed metal particles are absent. The metallic particles can be distributed on the surface of the polymeric shell in a substantially uniform manner.
[0097] [0097] The thickness of the film of the second metal can vary with the density of the particles of the first metal that are adsorbed on the polymeric shell of the microcapsule, with a higher density of the particles of the first metal typically promoting the growth of a thinner film. In some examples, the particles are deposited on the polymeric shell at a density such that said particles cover from 0.1 to 80% of the surface area of the polymeric shell, for example, from 0.5 to 40% of the surface area of the polymeric shell. polymeric shell, for example, from 1 to 4% of the surface area of the polymeric shell. The density of the particles in the polymeric shell can be determined using the procedure described in the Test Methods section here.
[0098] [0098] The particles of the first metal are preferably adsorbed on the polymeric shell: (i) adsorbing stabilized nanoparticles of charge of the first metal on the polymeric shell; (ii) adsorbing sterically stabilized nanoparticles of the first metal in the polymeric shell; or (iii) adsorbing particles of the first metal that are formed by in situ reduction. These methods are described in more detail below. Deposition of the first metal: adsorption of charge stabilized nanoparticles
[0099] [0099] In some examples, the particles of the first metal are charge-stabilized nanoparticles that are adsorbed on the polymeric shell. Charge stabilized nanoparticles are nanoparticles that comprise a charged species adsorbed on its surface. Since the stabilizer is a charged species, it will communicate a charged surface to the nanoparticles that can be exploited in order to adsorb the metallic particles to the surface of the polymeric shell. In some examples, the particles of the first metal are adsorbed onto the polymeric shell by electrostatic interaction.
[0100] [00100] The particles are preferably adsorbed on a surface modifying agent that forms part of the polymeric shell. The surface modifying agent can be adsorbed on and / or absorbed into the polymeric shell. Preferably, the polymeric shell was obtained by an emulsification process in which the surface modifying agent was used as an emulsifier, with the emulsifier being retained in the resulting shell. The surface modifying agent preferably has a charged surface that is used to attract and electrostatically adsorb the charge-stabilized nanoparticles to the polymeric shell.
[0101] [00101] In some examples, the particles of the first metal are charge stabilized by an anionic stabilizer. In some instances, the anionic stabilizer is selected from borohydride anions and citrate anions. In some instances, the anionic stabilizer is an anionic surfactant, for example, an anionic surfactant selected from sodium dodecyl sulfate, sodium laureth sulfate, dodecyl benzene sulfonic acid, perfluorooctane sulfonate, sodium dioctyl sulfosuccinate and sodium stearate. Preferably, the particles are stabilized with nanoparticles stabilized with borohydride or citrate.
[0102] [00102] In some examples, the particles of the first metal have a zeta potential of -20 mV to -150 mV, for example, from -30 mV to -90 mV.
[0103] [00103] Where the particles of the first metal are stabilized by an anionic stabilizer, it is preferable that the surface of the polymeric shell is neutral or cationic. In some examples, the polymeric shell has a substantially neutral surface having a zeta potential of -10 mV to +10 mV, for example, from -5 mV to +5 mV. In some examples, the polymeric shell has a positively charged surface, for example, having a zeta potential of +20 mV to +150 mV, for example, from +30 mV to +90 mV.
[0104] [00104] In some examples, the particles of the first metal are stabilized by an anionic stabilizer and the polymeric shell comprises a non-ionic surface modifying agent. In some instances, the surface modifying agent is a nonionic polymer, for example, a nonionic polymer selected from poly (vinyl alcohol) and poly (vinyl pyrrolidone).
[0105] [00105] In some examples, the particles of the first metal are stabilized by an anionic stabilizer and the polymeric shell comprises a cationic surface modifying agent. The surface modifying agent can be a cationic surfactant or a cationic polymer. Examples of cationic surfactants include, without limitation, alkyl ammonium surfactants such as cetyl trimethylammonium bromide, dodecyl dimethylammonium bromide, cetyl trimethylammonium chloride, benzalkonium chloride, cetylpyridinium chloride, dioctadyl dimethylammonium chloride and dimethylammonium chloride. Examples of cationic polymers include, without limitation, poly (diethylaminoethyl methacrylate), poly (dimethylaminoethyl methacrylate), poly (tertiary butylaminoethyl methacrylate) and di-block copolymers formed from a first block comprising a poly (aminoalkyl acrylate) and a second block comprising a poly (alkyl acrylate). Most preferably, the surface modifying agent is cetyl trimethylammonium bromide.
[0106] [00106] Alternatively, the particles of the first metal can be charge stabilized by a cationic stabilizer. Examples of cationic stabilizers include cationic surfactants such as quaternary ammonium surfactants, for example, cetyl trimethylammonium bromide, tetraoctylamonium bromide and dodecyl trimethylammonium bromide. Other quaternary ammonium surfactants include esterquats, that is, quaternary ammonium surfactants containing an ester group.
[0107] [00107] In some examples, the particles of the first metal have a zeta potential of +20 mV to +150 mV, for example, from +30 mV to +90 mV.
[0108] [00108] Where the particles of the first metal are stabilized by a cationic stabilizer, it is preferable that the surface of the polymeric shell is neutral or anionic. In some examples, the polymeric shell has a substantially neutral surface having a zeta potential of -10 mV to +10 mV, for example, from -5 mV to +5 mV. In some examples, the polymeric shell has a positively charged surface, for example, having a zeta potential of -20 mV to -150 mV, for example, from -30 mV to -90 mV.
[0109] [00109] In some examples, the particles of the first metal are stabilized by a cationic stabilizer and the polymeric shell comprises a non-ionic surface modifying agent. In some instances, the surface modifying agent is a nonionic polymer, for example, a nonionic polymer selected from poly (vinyl alcohol) and poly (vinylpyrrolidone).
[0110] [00110] In some examples, the particles of the first metal are stabilized by a cationic stabilizer and the polymeric shell comprises an anionic surface modifying agent. The surface modifying agent can be an anionic surfactant or an anionic polymer. Examples of anionic surfactants include, without limitation, sodium dodecyl sulfate, sodium laureth sulfate, dodecyl benzene sulfonic acid, sodium dioctyl sulfosuccinate, perfluorooctane sulfonate, sodium dioctyl sulfosuccinate and sodium stearate. Examples of anionic polymers include, without limitation, polyacids such as poly (acrylic acid) and poly (metracrylic acid).
[0111] [00111] The particles of the first metal can be alternatively charge stabilized by a zwitterionic stabilizer. In some instances, the zwitterionic stabilizer is a zwitterionic surfactant. Examples of zwitterionic surfactants include aminobetaines, imidazoline derivatives and phospholipids, for example, phosphatidyl choline.
[0112] [00112] Charge stabilized nanoparticles can be prepared using suitable procedures known in the art (see, for example, G. Frens, Nature, 1973, 241, 20 - 22). Such procedures will typically involve metal reduction ions in solution in the presence of a charged stabilizer. Thus, charge-stabilized nanoparticles can be obtained by providing a solution comprising ions of the first metal and a charged stabilizer, and reducing the ions to form metal particles that are charge-stabilized by the stabilizer.
[0113] [00113] In some examples, metal ions in solution are reduced by a reducing agent that becomes the stabilizer charged, for example, by sodium borohydride or by sodium citrate. By way of illustration, and without limitation, gold nanoparticles stabilized with borohydride can be prepared by contacting an aqueous solution of chlorouric acid with sodium borohydride.
[0114] [00114] The resulting charge stabilized nanoparticles can then be contacted with uncoated microcapsules under appropriate conditions, for example, at room temperature. The microcapsules can then be washed to remove any unbound particles.
[0115] [00115] Preferably, the ions of the first metal are present in the solution in a concentration of 0.005 to 50 mM, for example, from 0.01 to 20 mM, for example, from 0.05 to 5 mM. Preferably, the charged stabilizer is present in the solution at a concentration of 0.005 to 50 mM, for example, 0.01 to 20 mM, for example, 0.05 to 5 mM. Deposition of the first metal: adsorption of sterically stabilized nanoparticles
[0116] [00116] In some examples, the first metal is deposited by adsorbing sterically stabilized nanoparticles of the first metal on the surface of the polymeric shell. Sterically stabilized nanoparticles generally comprise a polymer or other macromolecule that is adsorbed onto the surface of the metal particles, forming a protective sheath around the particles and minimizing aggregation. The size of the steric stabilizer can be explored in order to adsorb the metallic particles on the surface of the polymeric shell. In some examples, the particles of the first metal are adsorbed on the polymeric shell by steric interaction.
[0117] [00117] In some examples, nanoparticles are sterically stabilized by a polymeric stabilizer. Preferably, the polymer comprises one or more groups selected from carboxyl, hydroxyl, amine, and ester groups. The polymer can be a homopolymer or a copolymer (for example, a graft copolymer or a block copolymer). Examples of suitable polymers include poly (ethylene oxide), polyethylene glycol, poly (acrylic acid), poly (acrylamide), poly (ethylene imine), poly (vinyl alcohol), carboxymethyl cellulose, chitosan, guar gum, gelatin, amylose, amylopectin , and sodium alginate.
[0118] [00118] Preferably the polymeric stabilizer has a weighted average molecular weight of at least 5 kDa, more preferably at least 10 kDa, more preferably at least 20 kDa. Preferably, the molecular weight of the polymeric stabilizer is 5 to 100 kDa, more preferably 10 to 80 kDa, more preferably 20 to 40 kDa.
[0119] [00119] In some examples, the polymeric stabilizer is a nonionic polymer. Examples of nonionic polymers include, without limitation, poly (vinyl alcohol), poly (vinyl propylene), poly (ethylene glycol) and poly (vinyl pyrrolidone). Poly (vinyl pyrrolidone) is particularly preferred as a steric stabilizer.
[0120] [00120] In some examples, the polymeric stabilizer is a cationic polymer. Examples of cationic polymers include, without limitation, polymers of poly (allyl amine), for example, poly (allyl amine hydrochloride).
[0121] [00121] In some examples, the polymeric stabilizer is an anionic polymer. Examples of anionic polymers include, without limitation, polyacids, for example, poly (acrylic acid) or poly (metracrylic acid).
[0122] [00122] In some examples, the nanoparticles are sterically stabilized by a polymeric surfactant. Examples of suitable surfactants include, without limitation, polyoxyalkylene glycol alkyl ethers (e.g., polyoxyethylene glycol alkyl ethers and polyoxypropylene glycol alkyl ethers), sorbitan esters (e.g., polysorbates), fatty acid esters, amine derivatives poly (isobutenyl) succinic anhydride and amine oxides.
[0123] [00123] As with the polymeric stabilizer, the polymeric surfactant preferably has a weighted average molecular weight of at least 5 kDa, more preferably at least 10 kDa, more preferably at least 20 kDa. Preferably, the polymeric surfactant has a weighted average molecular weight of 5 to 100 kDa, more preferably 10 to 80 kDa, more preferably 20 to 40 kDa.
[0124] [00124] The particles are preferably adsorbed on a surface modifying agent that forms part of the polymeric shell. The surface modifying agent can be adsorbed on and / or absorbed into the polymeric shell. Preferably, the polymeric shell was obtained by an emulsification process in which the surface modifying agent was used as an emulsifier, with the emulsifier being retained in the resulting shell. The sterically stabilized nanoparticles preferably bind through steric interactions to the surface modifying agent.
[0125] [00125] In some examples, the surface modifying agent is a non-ionic surface modifying agent, for example, a non-ionic surfactant or a non-ionic polymer. Examples of nonionic polymers include, without limitation, poly (vinyl alcohol) and poly (vinyl pyrrolidone). Most preferably, the non-ionic polymer is poly (vinyl alcohol).
[0126] [00126] In some examples, the surface modifying agent is a cationic surface modifying agent, for example, a cationic surfactant or a cationic polymer. Examples of cationic surfactants include, but are not limited to, cetyl trimethylammonium bromide, dodecyl dimethylammonium bromide, cetyl trimethylammonium chloride, benzalkonium chloride, cetylpyridinium chloride, dioctadecyl dimethylammonium chloride and dioctamethyl dimethyl bromide. Preferably, the cationic surface modifying agent is cetyl trimethylammonium bromide.
[0127] [00127] In some examples, the surface modifying agent is an anionic surface modifying agent, for example, an anionic surfactant or an anionic polymer. Examples of anionic surfactants include, without limitation, sodium dodecyl sulfate, sodium laureth sulfate, dodecyl benzene sulfonic acid, sodium dioctyl sulfosuccinate, perfluorooctane sulfonate, sodium dioctyl sulfosuccinate and sodium stearate. Examples of anionic polymers include, without limitation, polyacids such as poly (acrylic acid) and poly (metracrylic acid).
[0128] [00128] Suitable procedures for preparing sterically stabilized nanoparticles are known in the art (see, for example, Horiuchi et al., Surface and Coatings Technology, 2010, 204, 3811 - 3817). By way of illustration, sterically stabilized nanoparticles can be prepared by reducing metal ions in solution in the presence of a stabilizer.
[0129] [00129] Thus, in some examples, sterically stabilized nanoparticles are obtained by providing a solution comprising ions of the first metal and a stabilizer, and reducing the ions to form metal particles that are sterically stabilized by the stabilizer. Preferably, the ions of the first metal are present in the solution at a concentration of 0.01 to 100 mM, for example, 0.05 to 50 mM, for example, 0.1 to 10 mM. Preferably, the stabilizer is present in the solution at a concentration of 0.0001 to 1 mM, for example, from 0.005 to 0.5 mM, for example, from 0.001 to 0.1 mM.
[0130] [00130] The particles of the first metal can be adsorbed on the polymeric shell of the microcapsule by contacting the microcapsule with a fluid paste comprising said particles. Preferably, the metal nanoparticles are present in the slurry in an amount of more than 0.2% by weight and the slurry comprises less than 0.01% by weight of unbound stabilizer.
[0131] [00131] Contact can occur under ambient conditions. However, in order to facilitate the adsorption of particles on the surface of the microcapsule, the microcapsules can be heated in order to enhance the penetration of the sterically stabilized particles into the polymeric shell. Preferably, the microcapsules are heated to a temperature of 30 ° C to 80 ° C, for example, 40 ° C to 70 ° C. In some examples, the polymeric shell comprises an amorphous polymer and the microcapsule is heated to a temperature above the standard room temperature but below the glass transition temperature (Tg) of the polymer. Preferably, the elevated temperature is not more than 30 ° C below, for example, not more than 20 ° C below, the glass transition temperature of the amorphous polymer. Examples of amorphous polymers include, without limitation, polyacrylates, for example, poly (methyl methacrylate) and poly (ethyl methacrylate). The glass transition temperature of the polymer can be determined by differential scanning calorimetry (DSC) following ASTM E1356 ("Standard Test Method for Assignment of the Glass Transition Temperature by Differential Scanning Calorimetry"). Deposition of the first metal: deposition by reduction in situ
[0132] [00132] In some examples, the particles of the first metal are adsorbed onto the polymeric shell by contacting the uncoated microcapsule with a solution comprising ions of the first metal and a reducing agent. The presence of the reducing agent causes the ions of the first metal to be reduced in situ. As metal ions are reduced, they precipitate from the solution as metallic particles and seek to reduce the energy of the system by adsorbing on the polymeric shell of the microcapsule. The first metal can also be adsorbed on the polymeric shell of the microcapsule during the deposition process in the form of ions that have not been reduced by the reducing agent.
[0133] [00133] The reducing agent that is contacted with the uncoated microcapsule is preferably in solution. More preferably, the reducing agent is added to a solution comprising the metal ions and the uncoated microcapsule. Thus, the deposition of metallic particles on the surface of the microcapsule can be obtained by preparing an aqueous solution comprising ions of the first metal and uncoated microcapsules. A reducing agent is then added to the solution, resulting in the reduction of metal ions and the precipitation of particles of the first metal on the surface of the microcapsules. The reaction is allowed to progress for a sufficient time to allow the desired deposition of the metal particles on the surface of the microcapsule. The capsules can then be washed, separated from the other reagents and redispersed in water. The deposition process can be carried out at room temperature.
[0134] [00134] Preferably, the ions of the first metal are present in the solution in a concentration of 0.005 to 50 mM, for example, from 0.01 to 20 mM, for example, from 0.05 to 5 mM. Preferably, the reducing agent is present in the solution at a concentration of 0.05 to 500 mM, for example, from 0.1 to 200 mM, for example, from 0.5 to 50 mM.
[0135] [00135] The particles are preferably adsorbed on a surface modifying agent that is present in the polymeric shell. The surface modifying agent can be adsorbed on and / or absorbed into the polymeric shell. Preferably, the polymeric shell was obtained by an emulsification process in which the surface modifying agent was used as an emulsifier, with the emulsifier being retained in the resulting shell. The particles of the first metal can be adsorbed to the polymeric shell by one or more interactions selected from steric interactions and electrostatic interactions.
[0136] [00136] In some examples, the surface modifying agent is a nonionic surface modifying agent, for example, a nonionic polymer. Examples of nonionic polymers include, without limitation, poly (vinyl alcohol) and poly (vinyl pyrrolidone). Most preferably, the non-ionic polymer is poly (vinyl alcohol).
[0137] [00137] In some examples, the surface modifying agent is a cationic surface modifying agent, for example, a cationic surfactant or a cationic polymer. Examples of cationic surfactants include, but are not limited to, cetyl trimethylammonium bromide, dodecyl dimethylammonium bromide, cetyl trimethylammonium chloride, benzalkonium chloride, cetylpyridinium chloride, dioctadecyl dimethylammonium chloride and dioctamethyl dimethyl bromide. Preferably, the surface modifying agent is cetyl trimethylammonium bromide.
[0138] [00138] In some examples, the surface modifying agent is an anionic surface modifying agent, for example, an anionic surfactant or an anionic polymer. Examples of anionic surfactants include, without limitation, sodium dodecyl sulfate, sodium laureth sulfate, dodecyl benzene sulfonic acid, sodium dioctyl sulfosuccinate, perfluorooctane sulfonate, sodium dioctyl sulfosuccinate and sodium stearate. Examples of anionic polymers include, without limitation, polyacids such as poly (acrylic acid) and poly (metracrylic acid). Deposition of the second metal
[0139] [00139] Once the particles of the first metal have been adsorbed on the polymeric shell, a film of a second metal is formed on the particles of the first metal, thereby coating the polymeric shell with a continuous metallic film that surrounds the microcapsule. Preferably the thickness of the metallic coating is substantially uniform throughout the coating.
[0140] [00140] The metallic film is preferably formed by a non-electrical deposition process in which the deposition of the second metal is catalyzed by the adsorbed particles of the first metal. The non-electrical deposition process will generally comprise contacting microcapsules on which particles of the first metal have been deposited with an ion solution of the second metal in the presence of a reducing agent, in the absence of an electric current. The reducing agent is typically a mild reducing agent such as formaldehyde and non-electrical deposition is preferably carried out under alkaline conditions. Once the electroplating reaction begins, the deposition of the metallic coating can become autocatalytic. The thickness of the metallic film can be controlled by limiting the concentration of ions of the second metal in solution and / or the duration of the non-electrical deposition procedure.
[0141] [00141] Appropriate techniques for conducting the non-electrical deposition procedure are described, for example, in the following documents: Basarir et al., ACS Applied Materials & Interfaces, 2012, 4 (3), 1324 - 1329; Blake et al., Langmuir, 2010, 26 (3), 1533 - 1538; Chen et al., Journal of Physical Chemistry C, 2008, 112 (24), 8870 - 8874; Fujiwara et al., Journal of the Electrochemical Society, 2010, 157 (4), pp.D211-D216; Guo et al., Journal of Applied Polymer Science, 2013, 127 (5), 4186 - 4193; Haag et al., Surface and Coatings Technology, 2006, 201 (6), 2166 - 2173; Horiuchi et al., Surface & Coatings Technology, 2010, 204 (23), 3811 - 3817; Ko et al., Journal of the Electrochemical Society, 2010, 157 (1), pp.D46-D49; Lin et al., International Journal of Hydrogen Energy, 2010, 35 (14), 7555 - 7562; Liu et al., Langmuir, 2005, 21 (5), 1683 - 1686; Ma et al., Applied Surface Science, 2012, 258 (19), 7774 - 7780; Miyoshi et al., Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2008, 321 (1 - 3), 238 - 243; Moon et al., 2008, Ultramicroscopy, 108 (10), 1307 - 1310; Wu et al., Journal of Colloid and Interface Science, 2009, 330 (2), 359 - 366; Ye et al., Materials Letters, 2008, 62 (4 - 5), 666 - 669; and Zhu et al., Surface and Coatings Technology, 2011, 205 (8 - 9), 2985 - 2988.
[0142] [00142] By way of illustration, and without limitation, a silver film can be prepared by forming a dispersion comprising silver nitrate, formaldehyde, ammonia and microcapsules comprising particles of the first metal. The dispersion is then stirred for a sufficient period of time until a metallic film of the desired thickness is obtained. The capsules can then be washed, for example, by centrifugation, in order to separate them from the deposition solution.
[0143] [00143] The ions of the second metal are preferably present in the solution in a concentration of 0.05 to 2000 mM, for example, from 0.1 to 1750 mM, for example, from 0.5 to 1500 mM. Preferably, the reducing agent is present in the solution in a concentration of 0.05 to 3500 mM, for example, from 0.1 to 3000 mM, for example, from 0.5 to 2500 mM. Preferably, the second metal and the reducing agent are present in the solution in a molar ratio of second metal to reducing agent from 1:10 to 4: 1, for example, from 1: 5 to 2: 1, for example, from 1: 3 to 1: 1.
[0144] [00144] The non-electrical deposition process can be carried out at any suitable temperature, for example, a temperature from 0 to 80 ° C. Preferably, the non-electrical deposition process is carried out at room temperature. CHARACTERISTICS AND PROPERTIES OF COATED MICROCapsules
[0145] [00145] The coated microcapsules can be obtained in a range of different particle sizes. Preferably, the coated microcapsules have a particle size of at least 0.1 micron, more preferably at least 1 micron. Typically, the coated microcapsules will have a particle size of 500 microns or less, such as 100 microns or less, and more preferably 50 microns or less. Preferably, the coated microcapsules have a particle size of 0.1 to 500 microns, for example, 1 to 100 microns, for example, 1 to 30 microns, for example, 1 to 20 microns. The particle size of coated and uncoated microcapsules can be determined using the test procedure described in the Test Methods section here.
[0146] [00146] The coated microcapsules comprise a metallic coating having a maximum thickness of 1000 nm. The thickness of the metallic coating can be chosen such that the coated microcapsules break and release the encapsulated liquid core material under particular conditions, for example, under particular stresses. For example, when coated microcapsules comprise a perfume oil and form part of a fragrance formulation that is used by a user, the metallic coating may break during use, for example, due to rubbing the skin to which the formulation was applied . In this way, the perfume oil can be released in a controlled manner so that it is noticeable to the user for an extended period of time.
[0147] [00147] Conversely, it is also desirable that the metallic coating has a minimum thickness in order to reduce the likelihood of solvents permeating through the wall of the microcapsule and / or the metallic coating to break prematurely when the coated microcapsules are stored, transported or used. This is particularly important in the case of fine fragrance formulations, which will typically comprise a polar solvent such as ethanol in which the microcapsules are dispersed.
[0148] [00148] In some examples, the metallic coating has a maximum thickness of 500 nm, for example, a maximum thickness of 400 nm, for example, a maximum thickness of 300 nm, for example, a maximum thickness of 200 nm, for example , a maximum thickness of 150 nm, for example, a maximum thickness of 100 nm, for example, a maximum thickness of 50 nm. In some examples, the metallic coating has a minimum thickness of 1 nm, for example, a minimum thickness of 10 nm, for example, a minimum thickness of 30 nm. In some examples, the metallic coating has: a minimum thickness of 1 nm and a maximum thickness of 500 nm; a minimum thickness of 10 nm and a maximum thickness of 300 nm; or a minimum thickness of 10 nm and a maximum thickness of 200 nm. Preferably, the metallic coating has: a minimum thickness of 10 nm and a maximum thickness of 150 nm; a minimum thickness of 10 nm and a maximum thickness of 100 nm; a minimum thickness of 20 nm and a maximum thickness of 100 nm.
[0149] [00149] The coated microcapsules are designed to release their liquid core material when the microcapsules are broken. The rupture can be caused by forces applied to the shell during mechanical interactions. Microcapsules can have a fracture strength of about 0.1 MPa to about 25 MPa. The microcapsules preferably have a fracture resistance of at least 0.5 MPa. So that the microcapsules are easily friable, they preferably have a fracture resistance of less than 25 MPa, more preferably less than 20 MPa, more preferably less than 15 MPa. For example, microcapsules can have a fracture resistance of 0.5 to 10 MPa. The fracture resistance of the microcapsules can be measured according to the Fracture Resistance Test Method described in WO 2014/047496 (see pages 28 to 30 of this).
[0150] [00150] The coated microcapsules can be characterized in terms of their permeability. A coated microcapsule can retain more than 50% by weight of the liquid core material under the Ethanol Stability Test described here. More preferably, the coated microcapsule preferably retains more than 70% by weight of the liquid core material, for example, more than 80% by weight, for example, more than 85% by weight, for example, more than 90 % by weight, for example, more than 95% by weight, for example, more than 98% by weight, when tested under the Ethanol Loss Stability Test described here.
[0151] [00151] In some instances, the metallic coating is applied to an uncoated microcapsule that would otherwise retain less than 20% by weight of its liquid core material when tested under the Ethanol Loss Stability Test described here, for example example, less than 10%, for example, less than 5%, for example, less than 1%. COMPOSITIONS / ARTICLES
[0152] [00152] The coated microcapsules can be included in compositions (that is, products intended to be sold to consumers without further modification or processing). In some examples, the compositions may include from 0.001% to 99% by weight of the composition of the coated microcapsules, alternatively from 0.01% to 90% by weight of the composition of the coated microcapsules, alternatively from 0.1% to 75% by weight the composition of the coated microcapsules, alternatively from 0.1% to 25% by weight of the composition of the coated microcapsules, alternatively from 1% to 15% by weight of the composition of the coated microcapsules. The composition may include a mixture of coated microcapsules other than the present description, the mixture comprising a plurality of coated microcapsules comprising a first liquid core material and a plurality of coated microcapsules comprising a second liquid core material. Alternatively or in addition, the composition may comprise other microcapsules, for example, uncoated microcapsules, in addition to the coated microcapsules disclosed herein.
[0153] [00153] In some examples, at least 75%, 85% or even 90% by weight of the coated microcapsules in the composition have a particle size of 1 micron to 100 microns, more preferably 1 micron to 50 microns, even more preferably 10 microns to 50 microns, most preferably from 1 micron to 30 microns. Preferably, at least 75%, 85% or even 90% by weight of the coated microcapsules have a polymeric shell thickness from 60 nm to 250 nm, more preferably from 80 nm to 180 nm, even more preferably from 100 nm to 160 nm.
[0154] [00154] In some examples, the compositions are incorporated into consumer products (that is, products intended to be sold to consumers without further modification or processing). In addition, coated microcapsules can be applied to any article, such as a tissue or any absorbent material including, but not limited to, feminine hygiene products, diapers, and incontinence products for adults. The composition can also be included in an article, non-limiting examples of which include a dispenser / container. The compositions / articles disclosed here can be manufactured by combining the coated microcapsules disclosed here with the desired adjunct material to form the consumer product. The microcapsules can be combined with the adjunct material when the microcapsules are in one or more forms, including a slurry form, pure particle form, and spray dried particle form. The microcapsules can be combined with the adjunct material by methods that include mixing and / or spraying. The coated microcapsules can be formulated in any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. 5,879,584 which is incorporated herein by reference.
[0155] [00155] Equipment suitable for use in the processes disclosed here may include continuous agitation tank reactors, homogenizers, turbine agitators, recirculation pumps, paddle mixers, plow-type shear mixers, tape mixers, vertical axis granulators and drum mixers, both in batch process configurations and, where available, in continuous process configurations, spray dryers, and extruders. Such equipment can be obtained from Lodige GmbH (Paderbom, Germany), Littleford Day, Inc. (Florence, Kentucky, USA), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany), Niro (Soeborg, Denmark) , Hosokawa Bepex Corp. (Minneapolis, Minnesota, U.S.A.), Arde Barinco (New Jersey, U.S.A.).
[0156] [00156] Non-limiting examples of consumer products useful here include hair care products (human, dog, and / or cat), including bleach, colorant, dye, conditioner, growth, remover, growth retardant, shampoo, styler ; deodorants and antiperspirants; personal cleaning; color cosmetics; products, and / or methods referring to the treatment of the skin (human, dog, and / or cat), including application of creams, lotions, and other products topically applied for use by the consumer; and products and / or methods refer orally to materials administered to enhance the appearance of hair, skin, and / or nails (human, dog, and / or cat); shaving product; body spray; and fine fragrances such as colognes and perfumes; products for treating fabrics, hard surfaces and any other surfaces in the fabric and home care area, including: air care, car care, dishwashing detergent, fabric conditioner (including fabric softener), laundry detergent, additive and / or treatment for washing clothes and rinsing and / or, cleaning and / or hard surface treatment, and other cleaning for consumer or institutional use; products refer to disposable absorbent and / or non-absorbent articles including adult incontinence garments, bibs, diapers, training diapers, infant and baby wipes; hand soaps, shampoos, lotions, oral care tools (non-limiting examples including toothpaste, mouthwash, and dental whitening agents like Crest® Whitestrips®), and clothing; products such as wet or dry toilet paper, tissue paper, disposable tissues, disposable towels, and / or wipes; products refer to catamenial pads, adult incontinence pads, interlabial pads, panties liners, pessaries, sanitary wipes, tampons and tampon applicators, and / or wipes. PERSONAL CARE COMPOSITIONS
[0157] [00157] In some examples, the consumer product may be a personal care composition, that is, a composition intended to be applied anywhere on the human body and / or articles of clothing for any period of time. Non-limiting examples of personal care compositions include products such as those intended to treat and / or clean hair, styling products, deodorants and antiperspirants, personal cleaners, cosmetic products, products referring to skin treatment such as creams, lotions , and other products topically applied for use by the consumer; shaving products; hair coloring / bleaching products; body spray; and fine fragrances like colognes and perfumes. Personal care compositions can be manufactured by any method known in the art and packaged in any dispenser known in the art. In some examples, the personal care composition may include coated microcapsules and one or more adjunct materials. In some examples, personal care compositions include coated microcapsules and one or more adjunct materials, wherein the coated microcapsules comprise at least one perfume oil. In some examples, the personal care composition can include from about 0.01% to about 20% by weight of the microcapsule personal care composition. Some non-limiting examples of personal care compositions are described in more detail below. SHAMPOO COMPOSITION
[0158] [00158] The shampoo composition can comprise one or more detersive surfactants, which provide cleaning performance to the composition. The one or more detersive surfactants in turn can comprise an anionic surfactant, amphoteric or zwitterionic surfactants, or mixtures of these. Various examples and descriptions of detersive surfactants are presented in U.S. Patent No. 6,649,155; US Patent Application Publication № 2008/0317698; and US Patent Application Publication No. 2008/0206355, which are incorporated herein by reference in their entirety.
[0159] [00159] The concentration of the detersive surfactant component in the shampoo composition should be sufficient to provide the desired cleaning and foam performance, and generally ranges from about 2% by weight to about 50% by weight. The shampoo composition can also comprise a shampoo gel matrix, an aqueous carrier, and other additional ingredients described herein.
[0160] [00160] The shampoo composition can comprise a first aqueous carrier. Consequently, the shampoo composition formulations can be in the form of pourable liquids (under ambient conditions). Such compositions will therefore typically comprise a first aqueous carrier, which is present at a level of at least 20% by weight, from about 20% by weight to about 95% by weight, or from about 60% by weight to about 85% by weight. The first aqueous carrier may comprise water, or a miscible mixture of water and organic solvent, and in one aspect may comprise water with minimal concentrations or no significant concentration of organic solvent, except as otherwise incidentally incorporated into the composition as minor ingredients of others components.
[0161] [00161] The first aqueous carriers useful in shampoo composition include water and aqueous solutions of lower alkyl alcohols and polyhydric alcohols. The lower alkyl alcohols useful here are monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. The polyhydric alcohols useful here include propylene glycol, hexylene glycol, glycerin, and propane diol.
[0162] [00162] The shampoo composition described here can comprise a shampoo gel matrix. The shampoo gel matrix comprises (i) from about 0.1% to about 20% of one or more fatty alcohols, alternatively from about 0.5% to about 14%, alternatively from about 1% to about 10%, alternatively about 6% to about 8% by weight of the shampoo gel matrix; (ii) from about 0.1% to about 10% of one or more shampoo gel matrix surfactants, by weight of the shampoo gel matrix; and (iii) from about 20% to about 95% of an aqueous carrier, alternatively from about 60% to about 85% by weight of the shampoo gel matrix.
[0163] [00163] The fatty alcohols useful here are those having from about 10 to about 40 carbon atoms, from about 12 to about 22 carbon atoms, from about 16 to about 22 carbon atoms, or about 16 to about 18 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated. Non-limiting examples of fatty alcohols include, cetyl alcohol, stearyl alcohol, beenyl alcohol, and mixtures thereof. Mixtures of cetyl and stearyl alcohol in a ratio of about 20:80 to about 80:20 are suitable. Shampoo gel matrix surfactants can be a detersive surfactant.
[0164] [00164] The aqueous carrier may comprise water, or a miscible mixture of water and organic solvent, and in one aspect may comprise water with minimal concentrations or no significant concentration of organic solvent, except as otherwise incidentally incorporated into the composition as minor ingredients other components.
[0165] [00165] The aqueous carrier useful here includes water and aqueous solutions of lower alkyl alcohols and polyhydric alcohols. The lower alkyl alcohols useful here are monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. Exemplary polyhydric alcohols useful here include propylene glycol, hexylene glycol, glycerin, and propane diol. CONDITIONER COMPOSITION
[0166] The conditioner compositions described herein comprise (i) from about 0.025% to about 20% by weight of the conditioner composition, and (ii) a conditioner gel matrix. After applying a conditioner composition to the hair as described herein, the method then comprises rinsing the hair conditioner composition. The conditioner composition also comprises a conditioner gel matrix comprising (1) one or more high melting fatty compounds, (2) a cationic surfactant system, and (3) a second aqueous carrier.
[0167] [00167] The conditioner gel matrix of the conditioner composition includes a cationic surfactant system. The cationic surfactant system can be a cationic surfactant or a mixture of two or more cationic surfactants. The cationic surfactant system can be selected from: monolonged alkyl quaternized ammonium salt; a combination of mono-long alkyl quaternized ammonium salt and di-long alkyl quaternized ammonium salt; mono-long alkyl amidoamine salt; a combination of mono-long alkyl amidoamine salt and di-long alkyl quaternized ammonium salt, a combination of mono-long alkyl amindoamine salt and mono-long alkyl quaternized ammonium salt.
[0168] [00168] The cationic surfactant system can be included in the composition at a weight level of about 0.1% to about 10%, from about 0.5% to about 8%, from about 0.8 % to about 5%, and from about 1.0% to about 4%.
[0169] The conditioner gel matrix of the conditioner composition includes one or more high melting fatty compounds. The high-melting fatty compounds useful here may have a melting point of 25 ° C or higher, and are selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures of these . It is understood by the technician that the compounds disclosed in this section of the specification can, in some examples, fall into more than one classification, for example, some fatty alcohol derivatives can also be classified as fatty acid derivatives. However, a given classification is not intended to be a limitation on this particular compound, but it is done so for the convenience of classification and nomenclature. Furthermore, it is understood by the skilled person that, depending on the number and position of double bonds, and length and position of the branches, certain compounds having certain carbon atoms can have a melting point of less than 25 ° C. Such low melting point compounds are not intended to be included in this section. Non-limiting examples of high melting point compounds are found in the International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992.
[0170] [00170] Among a variety of high melting fatty compounds, fatty alcohols are suitable for use in the conditioner composition. The fatty alcohols useful here are those having from about 14 to about 30 carbon atoms, from about 16 to about 22 carbon atoms. These fatty alcohols are saturated and can be straight or branched alcohols. Suitable fatty alcohols include, for example, cetyl alcohol, stearyl alcohol, beenyl alcohol, and mixtures thereof.
[0171] [00171] Fatty compounds of high melting point of a single compound of high purity can be used. Unique compounds of pure fatty alcohols selected from the group of pure cetyl alcohol, stearyl alcohol, and beenyl alcohol can also be used. By "pure" here, what is meant is that the compound has a purity of at least about 90%, and / or at least about 95%. These unique compounds of high purity provide good rinsing ability of the hair when the consumer rinses the composition.
[0172] [00172] The high melting fatty compound can be included in the conditioner composition at a level of about 0.1% to about 20%, alternatively from about 1% to about 15%, and alternatively from about from 1.5% to about 8% by weight of the composition, due to providing improved conditioner benefits such as slippery feeling during application to damp hair, feeling of softness and hydration in dry hair.
[0173] The conditioner gel matrix of the conditioner composition includes a second aqueous carrier. Consequently, formulations of the conditioner composition can be in the form of pourable liquids (under ambient conditions). Such compositions will therefore typically comprise a second aqueous carrier, which is present at a level of about 20% by weight to about 95% by weight, or from about 60% by weight to about 85% by weight. The second aqueous carrier may comprise water, or a miscible mixture of water and organic solvent, and in one aspect may comprise water with minimal concentrations or no significant concentration of organic solvent, except as otherwise incidentally incorporated into the composition as minor ingredients of others components.
[0174] [00174] Second aqueous carriers useful in the conditioner composition include water and aqueous solutions of lower alkyl alcohols and polyhydric alcohols. The lower alkyl alcohols useful here are monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. The polyhydric alcohols useful here include propylene glycol, hexylene glycol, glycerin, and propane diol. RINSE-FREE TREATMENT
[0175] [00175] The rinse-free treatment described here can comprise from about 0.025% to about 0.25%, alternatively from about 0.05% to about 0.2%, alternatively from about 0.1% to about 0.15% of a compound selected from the group consisting of ethylenediamino-N, N'-disuccinic acid (EDDS), derivatives of ethylenediamino-N, N'-disuccinic acid (EDDS), salts of ethylenediamino-N, N ' -dissuccinic (EDDS), and mixtures of these, by weight of the treatment without rinsing. The rinse-free treatment also comprises (1) one or more rheology modifiers and (2) a third aqueous carrier. Treatment without rinsing can also include from about 0.025% to about 20%, alternatively from about 0.05% to about 0.5%, alternatively from about 0.1% to about 1% of microcapsules, weight of the treatment without rinsing.
[0176] [00176] Treatment without rinsing may include one or more rheology modifiers to adjust the rheological characteristics of the composition for better feel, properties in use and stability in suspension of the composition. For example, rheological properties are adjusted so that the composition remains uniform during storage and transport and does not drip unwantedly over other areas of the body, clothing or household furniture during use. Any suitable rheology modifier can be used. In one embodiment, treatment without rinsing may comprise from about 0.01% to about 3% of a rheology modifier, alternatively from about 0.1% to about 1% of a rheology modifier.
[0177] [00177] Treatment without rinsing may comprise a third aqueous carrier. Consequently, treatment formulations without rinsing can be in the form of pourable liquids (under ambient conditions). Such compositions will therefore typically comprise a third aqueous carrier, which is present at a level of at least 20% by weight, from about 20% by weight to about 95% by weight, or from about 60% by weight to about 85% by weight. The third aqueous carrier may comprise water, or a miscible mixture of water and organic solvent, and in one aspect may comprise water with minimal concentrations or no significant concentration of organic solvent, except as otherwise incidentally incorporated into the composition as minor ingredients of others components.
[0178] [00178] Third aqueous carriers useful in treatment without rinsing include water and aqueous solutions of lower alkyl alcohols and polyhydric alcohols. The lower alkyl alcohols useful here are monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. The polyhydric alcohols useful here include propylene glycol, hexylene glycol, glycerin, and propane diol. pH
[0179] [00179] The shampoo composition, conditioner composition, and / or treatment without rinsing can have a pH in the range of about 2 to about 10, at 25 ° C. The shampoo composition, conditioner composition, and / or treatment without rinsing can have a pH in the range of about 2 to about 6, alternatively about 3.5 to about 5, alternatively about 5.25 at about 7, which can help to solubilize copper and redox metals already deposited in the hair. ADDITIONAL COMPONENTS
[0180] [00180] The shampoo composition, conditioner composition, and / or rinse-free treatment (hair care compositions) described herein may optionally comprise one or more additional components known for use in hair care or personal care products, provided that the additional components are physically and chemically compatible with the essential components described here, or do not otherwise unduly harm the stability, aesthetics or performance of the product. Such additional components are most typically those described in reference records such as the CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1988, 1992. Individual concentrations of such additional components can vary from about 0.001% by weight to about 10% by weight of the hair care compositions.
[0181] [00181] Non-limiting examples of additional components for use in hair care compositions include conditioning agents (for example, silicones, hydrocarbon oils, fatty esters), natural cationic deposition polymers, synthetic cationic deposition polymers, anti- dandruff, particles, suspending agents, paraffinic hydrocarbons, propellants, viscosity modifiers, dyes, solvents or non-volatile diluents (water-soluble and water-insoluble), pearly auxiliaries, foam stimulators, additional non-ionic surfactants or co-surfactants, pediculocides, pH-adjusting agents, perfumes, preservatives, proteins, active skin agents, sunscreens, UV absorbers, and vitamins.
[0182] [00182] Hair care compositions are generally prepared by conventional methods as are known in the art of making the compositions. Such methods typically involve mixing the ingredients in one or more steps to a relatively uniform state, with or without heating, cooling, applying a vacuum, and the like. The compositions are prepared in such a way as to optimize stability (physical stability, chemical stability, photostability) and / or release of the active materials. The hair care composition can be in a single phase or a single product, or the hair care composition can be in separate phases or separate products. If two products are used, the products can be used together, at the same time or sequentially. Sequential use can occur in a short period of time, such as immediately after using a product, or it can occur over a period of hours or days. RINSE FORMULATIONS
[0183] [00183] The personal care composition can be a rinse formulation that can be applied topically to the skin and / or hair and rinsed off the skin and / or hair within minutes with water. The personal care composition can comprise a primary surfactant. Primary surfactants can comprise from 0.1% to 20%, from about 2% to about 10%, from about 5% to about 10%, or from about 2% to about 5% by weight of the composition of personal care. The primary surfactant may comprise one or more anionic surfactants. Personal care compositions can also comprise a secondary surfactant. Secondary surfactants can comprise from 0.1% to 20%, from about 2% to about 10%, or from about 2% to about 5% by weight of the personal care composition. Secondary surfactants can also comprise more than 20% by weight of the personal care composition. Personal care compositions can also contain about 20% to about 95%, about 40% to about 90%, about 60% to about 90%, or about 70% to about 90% water, by weight of the personal care composition. The personal care compositions may further comprise a viscosity modifier to modify the viscosity of the personal care composition. Such concentrations of viscosity modifiers can range, for example, from about 0.1% to about 10%, from about 0.3% to about 5.0%, from about 0.5% to about 10%, or from 0.5% to 3% by weight of personal care compositions. Personal care compositions can also include other adjunct personal care ingredients that can modify the physical, chemical, cosmetic or aesthetic characteristics of personal care compositions or serve as "active" components when deposited on the skin. Non-limiting examples of primary surfactants include sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, and ammonium laureth sulfate. Non-limiting examples of secondary surfactants include cocamidopropyl betaine. Non-limiting examples of other ingredients include fragrances and polyols. Non-limiting examples of viscosity modifiers include sodium carbonate, sodium chloride, sodium aluminum sulfate, disodium phosphate, sodium polymetaphosphate, sodium magnesium succinate, sodium sulfate, sodium tripolyphosphate, aluminum sulfate, aluminum chloride.
[0184] [00184] The rinse formulation can be a single-phase or a multi-phase product. Multiple-phase means that at least two phases here occupy separate but distinct physical spaces within the package in which they are stored, but are in direct contact with each other. The multi-phase product can have a cleaning phase and a benefit phase. The cleaning step may comprise a surfactant component comprising a surfactant or a mixture of surfactants. Non-limiting examples of these surfactants include anionic, nonionic, cationic, zwitterionic, and amphoteric surfactants, soap, and combinations thereof. The benefit phase can be anhydrous. The multi-phase product can also include a structured, non-foaming aqueous phase that comprises an aqueous structurant and water. The single-phase and / or multiple-phase product may also include other ingredients, non-limiting examples of which include humectants, occlusive agents, and fragrances. BODY SPRAYING / FINE FRAGRANCE
[0185] [00185] The personal care composition can be an aerosolized composition (that is, a composition intended to be aerosolized) as a body spray and / or fine fragrance. The aerosolized compositions described herein can include a volatile solvent or a mixture of volatile solvents.
[0186] [00186] Volatile solvents can comprise more than or equal to 10%, more than 30%, more than 40%, more than 50%, more than 60%, or more than 90%, and less than 99% by weight of the composition. A non-limiting example of a volatile solvent is ethanol. In some examples, the aerosolized composition may comprise from 0.01% to 98% by weight of the composition, of ethanol. The aerosolized composition can comprise a non-volatile solvent or a mixture of non-volatile solvents. Non-limiting examples of non-volatile solvents include benzyl benzoate, diethyl phthalate, isopropyl myristate, propylene glycol, dipropylene glycol, triethyl citrate, and mixtures thereof. "Non-volatile" refers to those materials that are liquid under ambient conditions and that have a measurable vapor pressure at 25 ° C. These materials typically have a vapor pressure less than about 0.01 mmHg, and a set point average boiling typically greater than about 250 ° C.
[0187] [00187] The aerosolized composition may also include one or more non-encapsulated fragrances. Generally, the fragrance (s) can be present at a level of about 0.01% to about 40%, from about 0.1% to about 25%, from about 0.25% to about 20%, or about 0.5% to about 15% by weight of the composition. Non-limiting examples of fragrances include alcohols, aldehydes, ketones, ethers, Schiff bases, nitriles, and esters. The compositions described here can include a carrier. Non-limiting examples of carriers include water, silicone oils such as D5 silicone, and other oils such as mineral oil, isopropyl myristate, and perfume oils. If present, the water can comprise from about 0.1% to about 40%, from about 1% to about 30%, or from about 5% to about 20% by weight, of the composition. In some examples, the aerosolized composition may include a propellant; non-limiting examples of propellants include compressed air, nitrogen, inert gases, carbon dioxide, gaseous hydrocarbons such as propane, n-butane, isobutene, cyclopropane, and mixtures thereof. In some instances, the aerosolized composition is aerosolized by the inherent design of the dispenser, such as by using a vortex chamber or other internal design. The aerosolized composition can also include other ingredients; non-limiting examples of which include an antiperspirant active (for use in a body spray) or other materials such as dyes (for use in a fine fragrance). In some examples, the aerosolized composition may be substantially free of a material selected from the group consisting of a propellant, a detersive surfactant, and combinations thereof. In some examples, the aerosolized composition includes one or more suspending agents as disclosed herein. In some examples, the aerosolized composition includes from 50% to 99.9% by weight of the composition, ethanol; optionally from 0.5% to 50% by weight of a fragrance composition; and optionally from 0.01% to about 15% by weight of the suspending agent composition. ANTIPERSPIRANT / DEODORANT
[0188] [00188] The personal care composition can be an antiperspirant / deodorant composition. The personal care composition may include an antiperspirant active suitable for application to human skin. The concentration of the antiperspirant active in the antiperspirant composition should be sufficient to provide the desired enhanced moisture protection. For example, the asset can be present in an amount of about 0.1%, about 0.5%, about 1%, or about 5%; about 60%, about 35%, about 25% or about 20% by weight of the antiperspirant composition. These weight percentages are calculated on an anhydrous metallic salt base exclusive of water and any complexing agents such as glycine, glycine salts, or other complexing agents. Personal care compositions can also include a structurant to help provide the personal care composition with the desired product viscosity, rheology, texture and / or hardness, or to help otherwise suspend any dispersed solids or liquids within the product. personal care composition. The term "structuring" can include any material known or otherwise effective in providing suspension, gelling, viscosification, solidification, or thickening properties to the personal care composition or that otherwise provide structure to the final product form. Non-limiting examples of structuring agents include, for example, gelling agents, polymeric or non-polymeric agents, inorganic thickening agents, or viscosifying agents. The concentration and type of structurant selected for use in the personal care composition may vary depending on the desired shape, viscosity, and product hardness. Personal care compositions can include a surfactant. A surfactant is generally present at a level of about 0.05% to about 5% by weight of the personal care composition, but can contain, from about 0.5% to about 5.0%; from about 1.0% to about 4%; from about 1.5% to about 3.5%; from about 1.75% to about 2.5%; about 2%, or any combination of these. Personal care compositions can also include anhydrous liquid carriers. The anhydrous liquid carrier can be present, for example, in concentrations ranging from about 10%, about 15%, about 20%, about 25%; about 99%, about 70%, about 60%, or about 50% by weight of the personal care composition. Such concentrations will vary depending on variables such as product shape, desired product hardness, and selection of other ingredients in the personal care composition. The anhydrous carrier can be any anhydrous carrier known for use in personal care compositions or otherwise suitable for topical application to the skin. For example, anhydrous carriers can include, but are not limited to, volatile and non-volatile fluids. The personal care composition can also include a bad odor reducing agent.
[0189] [00189] Bad odor reducing agents include components except the antiperspirant active within the personal care composition that act to eliminate the effect that body odor has on the display of fragrance. These agents can combine with unpleasant body odor so that they are not detectable including and can suppress the evaporation of bad body odor, absorb sweat or bad odor, mask bad odor, and / or prevent / inhibit microbiological activity from odor-causing organisms. The concentration of the bad odor reducing agent within the personal care composition should be sufficient to provide such chemical or biological means to reduce or eliminate body odor. Although the concentration varies depending on the agent used, generally, the bad odor reducing agent can be included within the personal care composition of about 0.05%, about 0.5%, or about 1%; about 15%, about 10%, or about 6% by weight of the personal care composition. Bad odor reducing agents may include, but are not limited to, pantothenic acid and its derivatives, petrolatum, menthyl acetate, uncomplexed cyclodextrins and derivatives thereof, talc, silica and mixtures thereof. Such agents can be used as described in U.S. 6,495,149, published by Scavone, et al and U.S. Patent Application 2003/0152539, filed January 25, 2002 in the names of Scavone, et al.
[0190] [00190] The personal care compositions described here may include a moisture-released fragrance technology delivery system that uses cyclic oligosaccharides, starches, starch derivatives, polysaccharide based encapsulation systems, and combinations thereof. As used herein, the term "cyclic oligosaccharide" means a cyclic structure comprising six or more units of saccharide. Cyclic oligosaccharides can have six, seven, or eight units of saccharide or mixtures thereof. It is common in the art to refer to cyclic oligosaccharides of six, seven and eight members as α, β, and γ, respectively. Cyclic oligosaccharides that may be useful include those that are soluble in water, ethanol, or both water and ethanol. The cyclic oligosaccharides useful here can have a solubility of at least about 0.1 g / 100 ml, at 25 ° C and 1 atm of pressure in water, ethanol, or both water and ethanol. The personal care compositions disclosed herein can comprise from about 0.001% to about 40%, from about 0.1% to about 25%, from about 0.3% to about 20%, from about 0 , 5% to about 10%, or from about 0.75% to about 5% by weight of the personal care composition, of a cyclic oligosaccharide. The personal care compositions disclosed here may comprise from 0.001% to 40%, from 1% to 25%, from 0.3% to 20%, from 0.5% to 10%, or from 0.75% to 5 % by weight of the personal care composition of a cyclic oligosaccharide.
[0191] [00191] Personal care compositions can include one or more fragrances. As used here, "fragrance" is used to indicate any odorous material. Any fragrance that is cosmetically acceptable can be used in the personal care composition. For example, the fragrance can be one that is a liquid at room temperature. Generally, the fragrance (s) can be present at a level of about 0.01% to about 40%, from about 0.1% to about 25%, from about 0.25% to about 20%, or about 0.5% to about 15% by weight of the personal care composition. Personal care compositions can also include other materials known for use in antiperspirant, deodorant or other personal care products, including those materials that are known to be suitable for topical application to the skin. Non-limiting examples include dyes or dyes, emulsifiers, dispensing agents, pharmaceuticals or other topical actives, conditioning agents or skin actives, deodorizing agents, antimicrobials, preservatives, surfactants, processing aids such as viscosity modifiers and washing aids. COSMETIC COMPOSITION
[0192] [00192] The personal care composition can take the form of a cosmetic composition that can be applied to mammalian keratinous tissue, including human skin. Cosmetic compositions can take various forms. For example, some non-limiting examples of forms include solutions, suspensions, lotions, creams, gels, tonic lotions, sticks, pencils, ointments, pastes, foams, powders, mousses, shaving creams, wipes, bands, plasters, electrically energized plasters , wound dressings and adhesive bandages, hydrogels, film-forming products, facial and skin masks, cosmetics (for example, bases, eyeliners, shadows), and the like.
[0193] [00193] For example, the cosmetic composition can comprise from about 1% to about 95% by weight of water. The cosmetic composition can comprise from about 1% to about 95% by weight of one or more oils. Oils can be used to solubilize, disperse, or carry materials that are not suitable for aqueous or water-soluble solvents. Suitable oils include silicones, hydrocarbons, esters, amides, ethers, and mixtures thereof. When the cosmetic composition is in the form of an emulsion, oils are carriers typically associated with the oily phase. The cosmetic composition can be in the form of a water-in-oil emulsion, an oil-in-water emulsion, or a water-in-silicone emulsion such that the cosmetic composition can include water, a silicone, oil, and combinations thereof. Cosmetic compositions can include an emulsifier. An emulsifier is particularly suitable when the cosmetic composition is in the form of an emulsion or if immiscible materials are being combined. The cosmetic composition can comprise from about 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, or 1% to about 20%, 10%, 5%, 3% , 2%, or 1% emulsifier. Emulsifiers can be non-ionic, anionic, zwitterionic, or cationic. Non-limiting examples of emulsifiers are disclosed in U.S. Patent 3,755,560, U.S. Patent 4,421,769, and McCutcheon's, Emulsifiers and Detergents, 2010 Annual Ed., Published by MC Publishing Co. Structuring agents can be used to increase viscosity, thicken, solidify, or provide solid or crystalline structure to the cosmetic composition. Structuring agents are typically grouped based on solubility, dispersibility, and phase compatibility. Examples of aqueous or water structuring agents include, but are not limited to, polymeric agents, natural or synthetic gums, polysaccharides, and the like. Cosmetic compositions can comprise from about 0.0001%, 0.001%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 5% to about 25%, 20%, 10%, 7%, 5%, 4%, or 2% by weight of the cosmetic composition, of one or more structuring agents. Cosmetic compositions may optionally contain one or more UV actives. As used here, "UV active" includes both sunscreens and physical sunscreens. Suitable UV assets can be organic or inorganic. Examples of some suitable UV assets are listed in the functional category of "sunscreen agents" in the Personal Care Product Council's International Cosmetic Ingredient Dictionary and Handbook, Thirteenth Edition, 2010. Cosmetic compositions can generally be prepared by conventional methods such as those known in the art. technique of making cosmetic compositions. Such methods typically involve mixing ingredients in one or more steps to a relatively uniform state, with or without heating, cooling, applying a vacuum, and the like. Typically, emulsions are prepared by first mixing the aqueous phase materials separately from the grease phase materials and then combining the two phases as appropriate to produce the desired continuous phase. Cosmetic compositions are preferably prepared in order to optimize stability (physical stability, chemical stability, photostability, etc.) and / or release of active materials. The cosmetic composition can be supplied in a packaging classified to store a sufficient amount of the cosmetic composition for a period of treatment. The size, shape, and design of the packaging can vary widely. Certain packaging examples are described in USPNs D570.707; D391,162; D516,436; D535,191; D542,660; D547,193; D547,661; D558,591; D563,221; 2009/0017080; 2007/0205226; and 2007/0040306.
[0194] [00194] The cosmetic compositions disclosed here can be applied to one or more surfaces of the skin and / or one or more surfaces of mammalian keratinous tissue as part of a user's daily routine or regimen. Additionally or alternatively, the cosmetic compositions here can be used on an "as needed" basis. In some instances, an effective amount of the cosmetic composition can be applied to the target portion of the keratinous tissue or skin. In some examples, the cosmetic composition may be provided in a package with written instructions detailing the application regime. HAIR COLORING / DECOLORING COMPOSITION
[0195] [00195] In some examples, the coated microcapsules can be incorporated into the personal care composition which is a color and / or hair bleaching composition. Such hair coloring compositions are often provided as a two-part form comprising a first component comprising the oxidizing agent and a second component comprising a surfactant system and if dyes are present, wherein the first and second components are mixed together before application. resulting composition on the consumer's hair. The coated microcapsules disclosed herein can be used to encapsulate one or more actives so as to provide a 1 part form comprising a first component comprising the oxidizing agent and a second component comprising a surfactant system and if dyes are present, in which at least one of the oxidizing agent, surfactant system, and dye is encapsulated using the coated microcapsules disclosed here. In some instances, the oxidizing agent (eg, inorganic peroxygen material capable of producing hydrogen peroxide in aqueous solution) is encapsulated in the coated microcapsules and included in the hair coloring / bleaching composition. In other examples, one or more adjunct materials are encapsulated within the coated microcapsules in order to provide a 1 part shape.
[0196] [00196] Non-limiting examples of adjunct materials for hair coloring / bleaching compositions include oxidizing agents such as water-soluble peroxygen oxidizing agents; alkyl glycosides such as a C6 to C16 alkyl glycoside which is comprised within the first composition or developer composition according to the formula R1-O- (G) xH wherein R1 is a linear or branched alkyl or alkenyl group comprising from 6 to 16 carbon atoms; associative polymers such as acrylic acid, metracrylic acid or itaconic acid; surfactants such as alkyl ether phosphates having an average of 1 to 20 ethylene oxide units; oxidative dye precursors or developers; preformed non-oxidative dyes; carbonate ion sources; additional thickeners and / or rheology modifiers; solvents; radical decontaminant; enzymes, additional surfactants; conditioning agents; carriers; antioxidants; stabilizers; chelators; permanent assets; perfume; beading agents; opacifiers; fluorescent dyes; reducing agents (thiolactic acid); hair swelling agents and / or polymers; gel network thickeners; cationic polymers such as polyquaternium 37, polyquaternium 7, polyquaternium 22, polyquaternium 87 and mixtures thereof; alkalizing agents such as those that provide a source of ammonium ions; couplers like phenols; direct dyes like acid yellow 1; conditioning agents such as silicones; radical decontaminants such as monoethanolamine; chelators such as EDDS (ethylene diaminedisuccinic acid); solvents such as water; and mixtures of these.
[0197] [00197] Any oxidizing agent known in the art can be used. Preferred water-soluble oxidizing agents are inorganic peroxygen materials capable of producing hydrogen peroxide in an aqueous solution. Water-soluble peroxygen oxidizing agents are well known in the art and include hydrogen peroxide, inorganic alkali metal peroxides such as sodium periodate and sodium peroxide and organic peroxides such as urea peroxide, melamine peroxide, and salt-decolorizing compounds inorganic perhydrate, such as the alkali metal salts of perborates, percarbonates, phosphates, persilicates, persulfates and the like. These inorganic perhydrated salts can be incorporated as monohydrates, tetrahydrates, etc. Alkyl and aryl peroxides, and or peroxidases can also be used. Mixtures of two or more of such oxidizing agents can be used if desired. The oxidizing agents can be supplied in an aqueous solution or as a powder that is dissolved before use. In some instances, the oxidizing agent is encapsulated within the coated particles. Non-limiting examples of preferred oxidizing agents are hydrogen peroxide, percarbonate (which can be used to provide a source of both oxidizing agent and carbonate ions), persulfates and combinations thereof. SUSPENSION AGENTS
[0198] [00198] The compositions described here may include one or more suspending agents to suspend the microcapsules (coated and / or uncoated microcapsules) and other material insoluble in water and / or insoluble in ethanol dispersed in the composition. The concentration of the suspending agent can vary from about 0.01% to about 90%, alternatively from about 0.01% to about 15% by weight of the composition, alternatively from about 0.5% to about 15%, alternatively from 0.1% to 15%.
[0199] [00199] Non-limiting examples of suspending agents include anionic polymers, cationic polymers, and nonionic polymers. Non-limiting examples of said polymers include vinyl polymers such as cross-linked acrylic acid polymers with the name CTFA Carbomer, cellulose derivatives and modified cellulose polymers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, nitro cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, arabic gum, tragacanth, galactana, locust bean gum, guar gum, karaya gum, carrage gum , pectin, agar, quince seed (Cydonia oblonga Mill), starch (rice, corn, potato, wheat), algae colloids (algae extract), microbiological polymers such as dextran, succinoglycan, pulleran, starch based polymers such such as carboxymethyl starch, methylhydroxypropyl starch, polymers based on alginic acid such as sodium alginate and alginic acid, propylene glycol esters col, acrylate polymers such as sodium polyacrylate, polyethylacrylate, polyacrylamide, and polyethyleneimine, and inorganic water-soluble material such as bentonite, aluminum and magnesium silicate, laponite, hectonite, and anhydrous silicic acid. Other suspending agents may include, but are not limited to, Konjac, Gellan, and a copolymer of methyl vinyl ether / maleic anhydride crosslinked with decadiene (e.g., Stabileze®).
[0200] [00200] Other non-limiting examples of suspending agents include cross-linked polyacrylate polymers such as Carbomers with the trade names Carbopol® 934, Carbopol® 940, Carbopol® 950, Carbopol® 980, Carbopol® 981, Carbopol® Ultrez 10, Carbopol® Ultrez 20 , Carbopol® Ultrez 21, Carbopol® Ultrez 30, Carbopol® ETD2020, Carbopol® ETD2050, Pemulen® TR-1, and Pemulen® TR-2, available from The Lubrizol Corporation; steareth-20 acrylates / methacrylate copolymer with the trade name ACRYSOLTM 22 available from Rohm and Hass; beheneth-25 acrylate / methacrylate copolymers, trade names including Aculyn-28 available from DOW, and VolarestTM FL available from Croda; acrylate copolymers under the trade name Aculyn 33 available from DOW; Peg150 / Decyl Alcohol / Smdi copolymer with the trade name Aculyn 44 available from DOW; nonoxynil hydroxyethylcellulose under the trade name AmercellTM POLYMER HM-1500 available from Amerchol; methylcellulose with the brand name BENECEL®, hydroxyethyl cellulose with the brand name NATROSOL®; hydroxypropyl cellulose with the trade name KLUCEL®; cetyl hydroxyethyl cellulose with the trade name POLISURF ® 67, supplied by Hercules; polymers based on ethylene oxide and / or propylene oxide with the trade names CARBOWAX® PEGs, POLIOX WASRs, and UCON® FLUIDS, all supplied by Amerchol; acryloyl ammonium dimethyltaurate / carboxyethylacrylate cross polymers as an Aristoflex® TAC copolymer, acryloyl ammonium / VP dimethyltaurate copolymers as an Aristoflex® AVS copolymer, acrylate acrylate dimethyltaurate copolymer as an acrylate / polyester acrylate / VP beheneth-25 ammonium / methacrylate such as Aristoflex® BVL or HMB, polyacrylate 11 cross-polymer such as Aristoflex Velvet, all available from Clariant Corporation; cross-linked polyacrylate polymer 6 with the trade name SepimaxTM Zen, available from Seppic; and cross-linked copolymers of vinyl pyrrolidone and acrylic acid such as the UltraThixTM P-100 polymer available from Ashland.
[0201] [00201] Other non-limiting examples of suspending agents include crystalline suspending agents that can be categorized as acyl derivatives, long chain amine oxides, and mixtures thereof.
[0202] [00202] Other non-limiting examples of suspending agents include ethylene glycol esters of fatty acids, in some respects those having from about 16 to about 22 carbon atoms; ethylene glycol stearates, both mono- and distearate, in some respects, the distearate containing less than about 7% of the monostearate; alkanol fatty acid amides, having from about 16 to about 22 carbon atoms, or about 16 to 18 carbon atoms, examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate; long-chain acyl derivatives including long-chain esters of long-chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); long chain esters of alkanol long chain amides (e.g., diethanolamide stearamide distearate, monoethanolamide stearamide stearate); and glyceryl esters (e.g., glyceryl distearate, trihydroxystearin, tribeenin), a commercial example of which is Thixin® R available from Rheox, Inc. Other non-limiting examples of suspending agents include long chain acyl derivatives, ethylene esters long chain carboxylic acid glycol, long chain amine oxides, and long chain carboxylic acid alkanol amides.
[0203] [00203] Other non-limiting examples of suspending agents include long-chain acyl derivatives including N, N-dihydrocarbeno benzoic acid and soluble salts thereof (e.g., Na, K), particularly N, N-di benzoic acid species (hydrogenated) C16, C18 and starch from this family, which are commercially available from Stepan Company (Northfield, I11., USA).
[0204] Non-limiting examples of long chain amine oxides suitable for use as suspending agents include alkyl dimethyl amine oxides (e.g., stearyl dimethyl amine oxide).
[0205] Other suitable non-limiting suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, examples of which include palmitamine or stearamine, and secondary amines having two fatty alkyl moieties each having at least about of 12 carbon atoms, examples of which include dipalmitoylamine or di (hydrogenated tallow) amine. Other non-limiting examples of suspending agents include di (hydrogenated tallow) phthalic acid amide, and crosslinked maleic anhydride-methyl vinyl ether copolymer. TISSUE AND HOME CARE COMPOSITIONS
[0206] [00206] In some examples, coated microcapsules are included in a tissue and home care product. As used herein, the term "tissue and home care product" is a cleaning and treatment composition that includes, unless otherwise stated, general purpose or "heavy duty" washing agents in granular or powder form ", especially cleaning detergents; liquid washing agents, in the form of widespread gel or paste, especially so-called heavy-duty liquid types; liquid fine fabric detergents; detergent agents for manual dishwashing or light-duty dishwashing detergents, especially those of the high foaming type; detergent agents for dishwashing by machine, including the various types of tablets, granular, liquid and rinse aid for domestic and institutional use; cleaning agents and liquid disinfectants, including antibacterial types for hand washing, cleaning bars, car or carpet shampoos, bathroom cleaners bathroom cleaners including toilet cleaners; and metal cleaners, fabric conditioning products including fabric softener and / or coolant that can be in liquid, solid and / or dryer sheet form; as well as cleaning aids such as bleaching additives and types of "anti-stain stick" or pre-treatment, products loaded with substrate such as sheets added to the dryer, dry and wet wipes and pads, non-woven substrates, and sponges; as well as sprays and mists. All such products that are applicable may be in standard, concentrated or even highly concentrated form as such products may in certain respects be non-aqueous.
[0207] [00207] The non-limiting list of adjunct materials illustrated below is suitable for use in compositions and may desirably be incorporated in certain aspects, for example to assist or enhance cleaning performance, for the treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, dyes, dyes or the like. The precise nature of these additional components, and their incorporation levels, will depend on the physical form of the composition and the nature of the tissue treatment operation for which it is to be used. Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersing agents, clay / anti-redeposition soil removal agents, rinse aid, foam suppressants, dyes, toners, perfumes, perfume release systems, structure elasticizing agents, carriers, structurants, hydrophores, auxiliaries process, solvents and / or pigments.
[0208] [00208] As stated, adjunct ingredients are not necessarily essential. Thus, certain aspects of the Applicants' compositions do not contain one or more of the following adjunct materials: surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide , hydrogen peroxide sources, preformed peracids, polymeric dispersing agents, clay / antiredeposition soil removal agents, rinse aid, foam suppressants, dyes, toners, perfumes, perfume release systems, structure elasticizing agents, carriers, hydrophores, auxiliaries process, solvents and / or pigments. PACKAGING
[0209] [00209] The coated microcapsules can be stored in any container or dispenser known in the art. Non-limiting examples of dispensers are described in EP0775530B1, EP1633490. METHOD OF USE
[0210] [00210] The personal care compositions disclosed herein can be applied to one or more surfaces of the skin and / or one or more surfaces of mammalian keratinous tissue as part of a user's daily routine or regimen. Additionally or alternatively, the compositions here can be used on an "as needed" basis and used as intended for the given consumer product. The composition can be applied to any article, such as a fabric, or any absorbent article including, but not limited to, feminine hygiene articles, diapers, and adult incontinence articles. For example, the compositions can be used as a body lotion, body spray, female spray, adult incontinence spray, baby spray, fine fragrance spray, or other spray. The size, shape, and aesthetic design of the dispensers described here can vary widely as the mechanical design of the dispenser. TEST METHODS Test method for measuring the size of microcapsules
[0211] [00211] The dimensions of uncoated and coated microcapsules can be measured using a Malvern Mastersizer Hydro 2000SM particle size analyzer. Measurements are performed according to British Standard BS ISO 13099-1: 2012 ("Colloidal systems - Methods for determining the zeta potential"). Test method for measuring the size of metal particles
[0212] [00212] The dimensions of the metallic particles can be measured by dynamic light scattering. Specifically, a Malvern Nano-ZS Zetasizer and FEI Tecnai TF20 (FEGTEM) electron microscopy adapted with HAADF detector and Gatan Orius SC600A CCD camera can be used. Test method for measuring the thickness of the polymeric shell and metallic coating
[0213] [00213] The thickness of the polymeric shell and metallic coating can be measured using microtome and FEGTEM. In order to prepare samples in cross section of capsule for TEM imaging, 1% of the washed capsules are centrifuged and redispersed in 1 ml of ethanol. The capsule samples are then air dried and mixed with EPO FIX epoxy resin. The sample is allowed to set overnight and microtome samples ~ 100 nm thick are suspended in water and fitted in TEM grids. FEGTEM is used to generate images of the microtomes and the thickness of the polymeric shell and metallic coating can be determined using a computer program, such as Image J. Test method to measure the adsorption density of metallic particles on the surface of the capsule
[0214] [00214] Metal particle surface adsorption densities can be measured directly from TEM images. Adsorption densities can be measured for small sample boxes on the surface of the capsule. The distance from the center of the sphere is then observed in each case. Each measurement was then both corrected for the curvature of the surface and divided evenly to compensate for the transparent nature of the capsules (TEM imaging shows the metal particles on both sides of the capsule). The size distribution of the capsules is then used to convert the numerical density obtained from these images to a 2D surface coverage (percentage). Test method for measuring zeta potentials of uncoated microcapsules, metallic particles and coated microcapsules
[0215] [00215] The zeta potentials of uncoated microcapsules, metallic particles and coated capsules can be analyzed using a Malvern nano-ZS zeta potential meter. Zeta potentials are measured according to British Standard BS ISO 13099-1: 2012 ("Colloidal systems - Methods for determining the zeta potential"). Test Method for analysis of chemical composition of coated microcapsules
[0216] [00216] The chemical composition of the coated microcapsules can be analyzed using an Oxford Instruments INCA 350 (EDX) energy dispersive X-ray spectroscopy with 80 mm X-Max SDD detector, which is installed in FEGTEM; and EDX in FEGTSEM. Ethanol Stability Test
[0217] [00217] The Ethanol Stability Test refers to the next test procedure.
[0218] [00218] A known volume of microcapsules (coated or uncoated microcapsules) is isolated and dispersed in an aqueous solution consisting of 1 part of water to 4 parts of absolute ethanol. The dispersion is heated to 40 ° C. After 7 days at 40 ° C, the microcapsules are isolated from the aqueous solution using centrifugation at 7000 rpm for 1 minute.
[0219] [00219] The aqueous solution is then subjected to analysis using gas chromatography to determine the content of the liquid core material that leached from the microcapsules. Samples are evaluated using a fused silica column 3 m in length and 0.25 mm internal diameter, coated with a 0.25 mm film of 100% dimethyl polysiloxane stationary phase. The column temperature is programmed to increase from 50 ° C to 300 ° C at a rate of 20 ° C per minute. A Clarus 580 gas chromatography is used for the analysis.
[0220] [00220] Where the loss of liquid core material from coated microcapsules is compared to uncoated microcapsules, uncoated microcapsules can be subjected to the washing steps of the coating procedure, to ensure that there is a loss of equivalent liquid core material from coated and uncoated microcapsules in advance of the Ethanol Stability Test.
[0221] [00221] To confirm the presence of the liquid core material within the coated microcapsules, a known sample of capsules is crushed between two glass slides and washed in a flask with 5 ml of ethanol. The capsules are isolated from the aqueous solution using centrifugation at 7000 rpm for 1 minute. The aqueous solution is then subjected to analysis using gas chromatography to determine the content of the liquid core material that leached out of the microcapsules. EXAMPLES
[0222] [00222] The following examples describe and illustrate modalities within the scope of the present invention. The Examples are provided for the purpose of illustration only and should not be construed as limitations of the present invention, since many variations of this are possible without departing from the spirit and scope of the invention. Unless otherwise stated, the test procedures used in these Examples are those specified in the Test Methods section of this specification. Example 1: Synthesis of microcapsules comprising a polyacrylate shell and an n-hexadecane core
[0223] [00223] The following procedure was used to prepare microcapsules comprising a polyacrylate shell and a nhexadecane core. Microcapsules were prepared by a coacervation procedure that involved oil-in-water emulsification followed by solvent extraction. Poly (vinyl alcohol) was used as an emulsifier.
[0224] [00224] 2.5 g of poly (methyl methacrylate) (PMMA, 99%, Sigma) was dissolved in 70.5 g of dichloromethane (DCM) (> 99%, Acros Organics). 5.0 g of n-hexadecane (99%, Acros Organics) was added to it and mixed until a phase formed. This formed the "core" phase. In a 100 ml volumetric flask, a 2% emulsifier solution was prepared by dissolving a sufficient amount of poly (vinyl alcohol) (PVA, 67 kDa, 8 to 88 Fluka) in Milli-Q water, to form the phase "to be continued". 7 ml of both the "core" and the "continuous" phase were added to a glass vial and emulsified using a homogenizer (IKA T25 Ultra-Turrax) at 15000 rpm for 2 min. The stabilized emulsion was then magnetically stirred at 400 rpm while 86 ml of the "continuous" phase was slowly poured. The diluted emulsion was then stirred at 400 rpm for 24 hours at room temperature to allow capsule formation to occur. The dispersion was transferred to a separatory funnel and the capsules allowed to form cream. The excess aqueous PVA phase was removed, and replaced with Milli-Q water three times. The capsules were redispersed in 50 ml of Milli-Q water. Example 2: Synthesis of microcapsules containing a polyacrylate shell and a toluene core
[0225] [00225] The following procedure was used to prepare microcapsules comprising a polyacrylate shell and a toluene core. Microcapsules were prepared by a coacervation procedure that involved oil-in-water emulsification followed by solvent extraction. Cetyl trimethylammonium bromide was used as an emulsifier.
[0226] [00226] 5 g of poly (ethyl methacrylate) (PEMA, 99%, Sigma) were dissolved in 81 g of dichloromethane (DCM) (> 99%, Acros Organics). 14 g of toluene (99%, Acros Organics) was added to it and mixed until a phase formed. This formed the "core" phase. In a 100 ml volumetric flask, a 0.28% emulsifier solution was prepared by dissolving a sufficient amount of trimethylammonium cetyl bromide (CTAB, 98%, Sigma) in Milli-Q water, to form the "continuous" phase ". 7 ml of both the "core" and the "continuous" phase were added to a glass vial and emulsified using a homogenizer (IKA T25 Ultra-Turrax) at 15000 rpm for 2 min. The stabilized emulsion was then magnetically stirred at 400 rpm while 86 ml of the "continuous" phase was slowly poured. The diluted emulsion was then stirred at 400 rpm for 24 hours at room temperature to allow capsule formation to occur. The capsules were isolated by washing by means of centrifugation (Heraeus Megafuge R16) and removal of the supernatant three times at 4000 rpm for 5 min. The capsules were redispersed in 25 ml of Milli-Q water. Example 3: Synthesis of microcapsules containing a polyacrylate shell and a hexyl salicylate core
[0227] [00227] The following procedure was used to prepare microcapsules comprising a polyacrylate shell and a hexyl salicylate core. Microcapsules were prepared by a coacervation procedure that involved oil-in-water emulsification followed by solvent extraction. Poly (vinyl alcohol) was used as an emulsifier.
[0228] [00228] 10 g of poly (methyl methacrylate) (PMMA, 99%, Sigma) were dissolved in 60 g of dichloromethane (DCM) (> 99%, Acros Organics). 30 g of hexyl salicylate (Procter and Gamble) was added to it and mixed until a phase formed. This formed the "core" phase. In a 100 ml volumetric flask, a 0.28% emulsifier solution was prepared by dissolving a sufficient amount of trimethylammonium cetyl bromide (CTAB, 98%, Sigma) in Milli-Q water, to form the "continuous" phase ". 7 ml of both the "core" and the "continuous" phase were added to a glass vial and emulsified using a homogenizer (IKA T25 Ultra-Turrax) at 15000 rpm for 2 min. The stabilized emulsion was then magnetically stirred at 400 rpm while 86 ml of the "continuous" phase was slowly poured. The diluted emulsion was then stirred at 400 rpm for 24 hours at room temperature to allow capsule formation to occur. The capsules were isolated by washing by means of centrifugation (Heraeus Megafuge R16) and removal of the supernatant three times at 4000 rpm for 5 min. The capsules were redispersed in 50 ml of Milli-Q water. Example 4: Preparation of stabilized gold charge nanoparticles
[0229] [00229] The following procedure was used to prepare gold nanoparticles stabilized with borohydride.
[0230] [00230] 0.34 g of HAuCl4 was dissolved in Milli-Q water in a 25 ml volumetric flask. 0.036 g of HCl was dissolved in Milli-Q water in a 25 ml volumetric flask. The HAuCl4 and HCl solutions were combined in a separate flask. 1.25 ml of this was added to the drops in 47.25 ml of Milli-Q water and stirred vigorously. A borohydride solution was prepared by adding 0.095 g of NaBH4 dissolved in 25 ml of Milli-Q water, to 0.1 g of NaOH dissolved in 25 ml of Milli-Q water. 1.5 ml of this was added all at once, and the solution was stirred for 1 minute. The solution changed the color from light yellow to dark red, indicating the formation of Au nanoparticles. Example 5: Adsorption of stabilized gold charge nanoparticles in microcapsules
[0231] [00231] The following procedure was used to adsorb the gold charge stabilized nanoparticles of Example 4 onto the surface of the microcapsules of Examples 2 and 3.
[0232] [00232] 5 ml of the Au nanoparticles were added to a beaker and stirred vigorously. 0.5 ml of microcapsules was added to the drops, and stirred vigorously for an additional 10 minutes. The microcapsules were collected by centrifugation (Heraeus Megafuge R16) and removal of the supernatant four times at 4000 rpm for 10 min, to remove excess nanoparticles, and then redispersed in water (2 ml). Example 6: Preparation of sterically stabilized platinum nanoparticles
[0233] [00233] The following procedure was used to prepare platinum nanoparticles stabilized with poly (vinyl pyrrolidone).
[0234] [00234] 0.5 g of poly (vinyl pyrrolidone) (PVP, 40 kDa, Fluka) was dissolved in 250 ml of Milli-Q water. 31.25 ml of this was added to a 1 L volumetric flask and filled to 1 L with Milli-Q water to provide a 0.00625 wt% PVP solution. 100 ml of this PVP solution was placed in a 250 ml conical flask and 0.23 g of H2PtCl6.6H2O was added and stirred until dissolved. A 0.5 mM NaBH4 solution was made by dissolving 0.189 g of NaBH4 in 10 ml of Milli-Q water. 0.4 ml of this was added to the platinum-PVP salt solution with vigorous stirring for 2 minutes. The solution immediately turned dark brown and was left to stand overnight to form Pt-PVP nanoparticles. Example 7: Adsorption of sterically stabilized platinum nanoparticles on microcapsules
[0235] [00235] The following procedure was used to adsorb the PVP-stabilized platinum nanoparticles of Example 6 onto the surface of the microcapsules of Examples 1 to 3.
[0236] [00236] 2 ml of capsules were added to 5 ml of platinum nanoparticles stabilized with PVP in a 40 ml glass vial, and mixed in a carousel for 10 min. The capsules were then washed by centrifugation at 4000 rpm for 5 minutes, three times. The capsules were redispersed in 30 ml of Milli-Q water. Example 8: Adsorption of platinum nanoparticles on microcapsules by in situ reduction
[0237] [00237] The following procedure was used to adsorb platinum nanoparticles by means of in situ reduction on the surface of the microcapsules of Examples 1 to 3.
[0238] [00238] In a 100 ml volumetric flask, 0.023 g of H2PtCl6.6H2O was dissolved in Milli-Q water up to 100 ml. 50 ml of this was placed in a conical flask and 1.25 ml of capsules was added and stirred vigorously for 30 min. 0.075 g of NaBH4 (Aldrich) was dissolved to 100 ml with Milli-Q water. 50 ml of this was added to the drops. Vigorous stirring was continued for 30 min. The capsules were then washed by separation for 72 h, allowing the excess Pt to settle and the capsules to form cream. Excess Pt and water were removed using a 50 ml pipette and the capsules were redispersed in 7.5 ml of Milli-Q water. Example 9: Formation of silver film by non-electrical deposition
[0239] [00239] The following procedure was used to form a continuous silver film on the microcapsules of Example 5 by non-electrical deposition.
[0240] [00240] 2 ml of microcapsules were added to a beaker containing 47.5 ml of Milli-Q water. 0.5 ml of 0.1M AgNO3 (99%, Sigma) was added and stirred vigorously. Then, 50 µl of formaldehyde (35% in H2O, Sigma) was added, followed by 26 µl of ammonia (25% in H2O, Sigma) to control the pH to ~ 10, providing a silver-gray dispersion. The dispersion was then stirred for 10 min after which it was centrifuged at 4000 rpm for 10 min, 3 times, for washing, replacing the supernatant each time with Milli-Q water. Example 10: Gold foil formation by non-electrical deposition
[0241] [00241] The following procedure was used to form a continuous gold film on the surface of the microcapsules of Examples 7 and 8 by non-electrical deposition.
[0242] [00242] 1.58 g of HAuCl4 (99.9%, Sigma) was dissolved to 100 ml with Milli-Q water. 0.58 g of hydrogen peroxide (35% in water, Aldrich) was dissolved to 100 ml with Milli-Q water. 0.2 g of poly (vinyl pyrrolidone) was dissolved to 100 ml with Milli-Q water. 1 ml of each of the above solutions was added to a 40 ml glass vial to form the deposition solution. 7.5 ml of the microcapsules were added to the drops in the deposition solution and stirred vigorously for 5 min. The capsules were washed by centrifugation at 4000 rpm for 5 minutes, three times. Example 11: Characterization of microcapsules comprising a metallic Pt / Au coating
[0243] [00243] Coated microcapsules comprising a PMMA shell, a hexadecane core and a metallic coating comprising a gold film arranged in a layer of platinum nanoparticles were prepared following the procedures described in examples 1, 8 and 10. The coated microcapsules were then characterized using SEM and TEM.
[0244] [00244] Figure 2a is an SEM image of the uncoated PMMA microcapsules. Figure 2b is a TEM image showing the platinum nanoparticles adsorbed on the outer surface of the PMMA microcapsules. Figure 2c is an image of SEM showing the continuous gold film.
[0245] [00245] The maximum thickness of the metallic coating was less than 200 nm in this example, but it will be appreciated that the thickness of the coating can be varied. Example 12: Characterization of microcapsules comprising an Au / Ag metallic coating
[0246] [00246] Coated microcapsules comprising a PEMA shell, a toluene core and a metallic coating comprising a silver film arranged in a layer of gold nanoparticles stabilized with borohydride were prepared following the procedures described in examples 2, 4, 5 and 9 The coated microcapsules were then characterized using optical microscopy, SEM, TEM and EDX.
[0247] [00247] Figure 3a is an optical micrograph showing the uncoated PEMA microcapsules. Figure 3b is a TEM image showing the gold nanoparticles stabilized with borohydride adsorbed on the surface of the microcapsules. Figure 3c is an image of SEM showing the continuous silver film. Figure 3d is an EDX graph of the silver film. The maximum thickness of the metallic coating was 140 nm in this example, but it will be appreciated that the thickness of the coating can be varied. Reference is made in this respect to Figures 4 and 5, which illustrate that the thickness of the metallic coating can be modified, for example, by varying the concentration of silver ions in the non-electrical deposition solution. Example 13: Characterization of microcapsules comprising a metallic coating of Pt / Au
[0248] [00248] Coated microcapsules comprising a PMMA shell, a hexyl salicylate core and a metallic coating comprising a gold film arranged in a layer of platinum nanoparticles with PVP stabilized were prepared following the procedures described in examples 3, 6, 7 and 9. The coated microcapsules were then characterized using optical microscopy, SEM and TEM.
[0249] [00249] Figure 6a is an optical micrograph showing the uncoated PMMA microcapsules. Figure 6b is a TEM image showing the platinum nanoparticles stabilized with PVP adsorbed on the surface of the microcapsules. Figure 6c is an image of SEM showing the gold film in the microcapsules. The maximum thickness of the metallic coating was less than 100 nm in this example, but it will be appreciated that the thickness of the coating can be varied. Example 14: Performance of coated microcapsules under the Ethanol Stability Test
[0250] [00250] Coated microcapsules comprising a PMMA shell, a hexadecane core and a metallic coating comprising a layer of platinum nanoparticles and a continuous gold film disposed therein were prepared following the procedures described in examples 1, 8 and 10. The microcapsules coated cells were then tested for their ability to retain liquid core material using the Ethanol Stability Test described here, and their performance was compared to that of uncoated PMMA microcapsules.
[0251] [00251] Figure 7a is a graph showing the performance of coated PMMA and uncoated PMMA microcapsules under the Ethanol Stability Test (see data points indicated as squares and diamonds respectively). Also shown in Figure 7a is a data point obtained after the fracture of the coated PMMA microcapsules at the end of the experiment (see the data point indicated as a triangle), confirming that the liquid core material has been encapsulated. The fractured microcapsules are shown in Figure 7b. It can be seen from these data that the coated microcapsules exhibited negligible leakage of the liquid core material. In contrast, more than 50% of the liquid core material leaked from the uncoated microcapsules after one day. Example 15: Synthesis of microcapsules comprising a melamine formaldehyde shell and a soybean oil core
[0252] [00252] The following procedure was used to prepare microcapsules comprising a melamine formaldehyde shell and a liquid core comprising soybean oil. Microcapsules were prepared by an in situ polymerization process in which a copolymer of butyl acrylate-acrylic acid and poly (vinyl alcohol) were used as emulsifiers.
[0253] [00253] 0.9 g of butyl acrylate-acrylic acid copolymer (Colloid C351, 2% solids, Kemira), and 0.9 g of poly (acrylic acid) (PAA, 100 kDa, 35% in Sigma water ) were dissolved in 20 g of Milli-Q water. An amount of sodium hydroxide was added to this solution to adjust the pH to 3.5.
[0254] [00254] 0.65 g of partially methylated methylol melamine resin (Cymel 385, 80% solids, Cytec) and 20 g of hexyl salicylate were added while mixing at 1000 rpm for 60 minutes. In a separate container, 1.0 g of acrylic butyl acid acrylate copolymer was mixed with 2.5 g of methylol melamine resin partially methylated in 12 g of Milli-Q water. An amount of sodium hydroxide was added to this to adjust the pH to 4.6. This was added to the main mixture along with 0.4 g of sodium sulfate (Sigma). The mixture was heated to 75 ° C and the temperature maintained for 6 h with continuous stirring at 400 rpm. Example 16: Synthesis of microcapsules comprising a polyacrylate shell and a core comprising soybean oil and isopropyl myristate
[0255] [00255] The following procedure was used to prepare microcapsules comprising a polyacrylate shell and a liquid core comprising soybean oil and isopropyl myristate. Microcapsules were prepared by an interfacial polymerization procedure in which poly (vinyl pyrrolidone) was used as an emulsifier.
[0256] [00256] 15.0 g of hexyl acetate were mixed with 3.75 g of isopropyl myristate at 400 rpm until a homogeneous solution was obtained. 15.0 g of the solution were placed in a three-necked round-bottom flask and mixed at 1000 rpm using a magnetic stirrer.
[0257] [00257] The temperature was increased to 35 ° C, then 0.06 g of 2,2-azobis-2,4-dimethyl-pentanonitrile (Vazo-52, Du Pont) and 0.02 g of 2,2-azobis (2-methylbutyronitrile) (Vazo-67, Du Pont) were added to the reactor, with a blanket of nitrogen applied at 100 cm3.min-1. The temperature was raised to 75 ° C and maintained for 45 minutes before being cooled to 60 ° C slowly.
[0258] [00258] The remaining oil-myristate solution was mixed with 0.05 g of t-butylaminoethyl methacrylate (Sigma), 0.04 g of 2-carboxyethyl acrylate (Sigma), and 1.95 g of urethaneacrylate oligomer hexafunctional aromatic (CN9161, Sartomer) at 400 rpm, until homogeneous. The mixture was degassed using nitrogen. At 60 ° C, this mixture was added to the reaction vessel and held at 1000 rpm at 60 ° C for 10 minutes, before stirring was stopped.
[0259] [00259] 2.0 g of poly (diallyl dimethyl ammonium chloride) (pDADMAC, 32% active, Sigma) were dissolved in 23.6 ml of Milli-Q water. 0.11 g of 20% sodium hydroxide solution, then 0.12 g of 4,4-azobis (cyanovaleric acid) (Vazo-68 WSP, Du Pont) was added and stirred at 400 rpm until it dissolved.
[0260] [00260] The oil-monomer solution was added to the pDADMAC solution. The mixture was then restarted at 1000 rpm for 60 minutes. The mixture was then slowly heated to 75 ° C and maintained at this temperature for 12 h with stirring at 400 rpm. Example 17: Preparation of stabilized gold charge nanoparticles
[0261] [00261] The following procedure was used to prepare gold nanoparticles stabilized with borohydride.
[0262] [00262] 0.34 g of HAuCl4 was dissolved in Milli-Q water in a 25 ml volumetric flask. 0.036 g of HCl was dissolved in Milli-Q water in a 25 ml volumetric flask. The HAuCl4 and HCl solutions were combined in a separate flask. 1.25 ml of this was added to the drops in 47.25 ml of Milli-Q water and stirred vigorously. A borohydride solution was prepared by adding 0.095 g of NaBH4 dissolved in 25 ml of Milli-Q water, to 0.1 g of NaOH dissolved in 25 ml of Milli-Q water. 1.5 ml of this was added all at once, and the solution was stirred for 1 minute. The solution changed the color from light yellow to dark red, indicating the formation of Au nanoparticles. Example 18: Adsorption of gold-charge stabilized nanoparticles into microparticles
[0263] [00263] The following procedure was used to adsorb the gold charge stabilized nanoparticles of Example 17 on the surface of the microcapsules of Examples 15 and 16.
[0264] [00264] 5 ml of the Au nanoparticles were added to a beaker and stirred vigorously. 2 ml of microcapsules were added to the drops, and shaken vigorously for an additional 10 minutes. The microcapsules were collected by centrifugation (Heraeus Megafuge R16) and removal of the supernatant four times at 4000 rpm for 10 min to remove excess nanoparticles, and were then redispersed in water (20 ml). Example 19: Formation of silver film by non-electrical deposition
[0265] [00265] The following procedure was used to form a continuous silver film on the microcapsules of Example 18 by non-electrical deposition.
[0266] [00266] 5 ml of microcapsules were added to a beaker containing 30 ml of Milli-Q water. 0.5 ml of 0.1M AgNO3 (99%, Sigma) was added and stirred vigorously. Then 50 µl of formaldehyde (35% in H2O, Sigma) was added, followed by 26 µl of ammonia (25% in H2O, Sigma) to control the pH to ~ 10, providing a silver-gray dispersion. The dispersion was then stirred for 10 min after which it was centrifuged at 4000 rpm for 10 min, 3 times, for washing, replacing the supernatant each time with Milli-Q water. Example 20: Characterization of microcapsules comprising a melamine formaldehyde shell and an Au / Ag metallic coating
[0267] [00267] Coated microcapsules comprising a melamine formaldehyde shell, a soy oil core and a metallic coating comprising a silver film arranged in a layer of gold nanoparticles stabilized with borohydride were prepared following the procedures described in examples 15 and 17 to 19. The coated microcapsules were then characterized using optical microscopy, SEM, TEM and EDX.
[0268] [00268] The coated microcapsules were then tested for their ability to retain liquid core material using the Ethanol Stability Test described here, and their performance was compared to that of uncoated melamine formaldehyde microcapsules. While the coated microcapsules exhibited negligible leakage of the liquid core material, more than 50% of the liquid core material leaked from the uncoated microcapsules after one day. Example 21: Characterization of microcapsules comprising a polyacrylate shell and a metallic Au / Ag coating
[0269] [00269] Coated microcapsules comprising a polyacrylate shell, a core containing hexyl acetate and isopropyl myristate, and a metallic coating comprising a silver film arranged in a layer of gold nanoparticles stabilized with borohydride were prepared following the procedures described in the examples 16 to 19. The coated microcapsules were then characterized using optical microscopy, SEM, TEM and EDX.
[0270] [00270] The coated microcapsules were then tested for their ability to retain liquid core material using the Ethanol Stability Test described here, and their performance was compared to that of uncoated polyacrylate microcapsules. While the coated microcapsules exhibited negligible leakage of the liquid core material, more than 50% of the liquid core material leaked from the uncoated microcapsules after one day. Example 22: Fine fragrance composition
[0271] [00271] A gold coating is placed on the surface of a melamine formaldehyde wall perfume microcapsule (MFPMC). There are generally two steps. The first step is the addition of Pt to coat the surface of the MF-PMC. The second step is the addition of Au to the surface of MF-PMC coated with Pt. Finally, scanning electron microscopy (SEM) images are provided.
[0272] [00272] MF-PMC is generally manufactured in accordance with U.S. 8,940,395 and available from Appleton Papers Inc. (USA). MF-PMC is supplied as a spray dried powder. Fracture strength data for this MF-PMC is 1 to 3 MPa as measured before being spray dried on a powder. It is not known whether spray drying impacts fracture resistance. The target particle size for the MF-PMC is 18 microns (volumetric weighted median particle size) that is, the largest number of MF-PMC (by volume) is at a particle size of 18 microns.
[0273] [00273] The first step is conducted as a method of reduction in situ or as a method of adsorption of sterically stabilized Pt nanoparticles. The in situ method is described. The addition of Pt to the surface of the MF-PMC is described. 500 mg of MF-PMC particles are dispersed in 20 g of water and sonicated for 30 minutes to suspend particles and break up the aggregates. 0.23 g of H2PtCl6 is dissolved in 100 ml of water. 0.076 g of NaBH4 is dissolved in 100 ml of water. 2 ml of MF-PMC dispersion is added to 25 ml of H2PtCl6 solution and stirred for 30 mins. 25 mL of NaBH4 is then added and stirred using a magnetic stirrer for an additional 90 min. The resulting suspension is centrifuged (4000 rpm for 10 min) and washed with 25 ml of distilled water. The process is repeated 2 more times.
[0274] [00274] The adsorption method is described. First, a Pt nanoparticle suspension is manufactured. 0.23 g of H2PtCl6 is dissolved in 100 ml of poly (vinyl pyrrolidone) ("PVP") (1.56 µM) 0.4 ml of NaBH4 (0.2 M) is added and the suspension stirred at high speed for 2 minutes. The nanoparticle suspension is then left to stand overnight. Second, the nanoparticle suspension is added to the MF-PMC. 500 mg of the MFPMC particles are dispersed in 20 g of water and sonicated for 30 min to suspend particles and break up the aggregates. 5 ml of the Pt nanoparticle suspension is diluted an additional 5 ml of water. 1 ml of the MF-PMC particle suspension is added to the diluted Pt nanoparticle suspension. The combined suspensions are allowed to stir for 60 minutes on a merry-go-round. Subsequently, the resulting suspension is centrifuged (4000 revolutions per minute (rpm) for 10 minutes) and washed with 25 ml of distilled water. The process is repeated 2 more times.
[0275] [00275] The second stage of the MF-PMC surface coated with Au on Pt coating is described. This second stage is the same regardless of the method used in the first stage. 1 ml of HAuCl4 (40 mM), 1 ml of H2O2 (60 mM) and 3 ml of PVP (0.2% by weight) are added to a glass vial. 1 mL of MF-PMC coated with a nanoparticle is added to it and stirred on a merry-go-round for 10 minutes. The resulting suspension is centrifuged (4000 rpm for 5 minutes) and washed with 25 ml of distilled water. The process is repeated 2 more times.
[0276] [00276] As can be seen in the SEM images of Figures 8 and 9, a gold coating is obtained for the MF-PMC. Figure 8 is the in situ reduction method, ostensibly obtaining a full gold coating. Figure 9 is the PVP-stabilized method where the surface of the MF-PMC gets a gold coating.
[0277] [00277] It should be understood that each maximum numerical limitation provided throughout this specification includes each lower numerical limitation, as if such lower numerical limitations were expressly written here. Each minimum numerical limitation provided throughout this specification will include each upper numerical limitation, as if such upper numerical limitations were expressly written here. Each numerical range provided throughout this specification will include each narrower numerical range that falls within such a wider numerical range, as if such narrower numerical ranges were all expressly written here.
[0278] [00278] The dimensions and values disclosed here should not be understood as being strictly limited to the exact numerical values reported. In fact, unless otherwise specified, each such dimension is intended to mean both the reported value and a functionally equivalent range surrounding this value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
[0279] [00279] Each document cited here, including any patent or cross-reference or related application and any patent or patent application to which this application claims priority or benefit thereof, is hereby incorporated by reference in its entirety unless expressly expressed. excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, shows, suggests or discloses any such invention. In addition, as any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document must control.
[0280] [00280] Although particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

权利要求:
Claims (12)
[0001]
Consumer product, characterized by the fact that it comprises a composition, said composition comprising: an adjunct material, which is selected from surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, pre-peracids formed, polymeric dispersing agents, clay / anti-redeposition soil removal agents, rinse aid, foam suppressants, dyes, toners, perfumes, perfume release systems, structure elasticizing agents, carriers, structuring agents, hydrotropes, processing aids, solvents and / or pigments; and a plurality of coated microcapsules, said coated microcapsule comprising i) a microcapsule comprising a polymeric shell and a liquid core material encapsulated therein; wherein the polymeric shell is obtained by an emulsification process in which a surface modifying agent is used as an emulsifier; and ii) a metallic coating surrounding said microcapsule; wherein the metallic coating comprises particles of a first metal adsorbed on said polymeric shell and a film of a second metal formed thereon; and where the metallic coating has a maximum thickness of 1000 nm, wherein the polymeric shell comprises a surface modifying agent; and wherein at least some of the particles are adsorbed onto said surface modifying agent, wherein the surface modifying agent is selected from a polymer or a surfactant; or it is selected from cetyl trimethylammonium bromide (CTAB), poly (vinyl alcohol) (PVA), poly (vinyl pyrrolidone) (PVP), and mixtures of these.
[0002]
Consumer product according to claim 1, characterized by the fact that the liquid core material is selected from the group consisting of perfumes; rinse aid; insect repellents; silicones; waxes; flavors; vitamins; fabric softening agents; depilatories; skin care agents; enzymes; probiotics; dye and polymer conjugate; dye and clay conjugate; perfume delivery system; sensates; attractive; antibacterial agents; dyes; pigments; bleaches; flavoring; sweeteners; waxes; pharmaceutical products; fertilizers; herbicides and mixtures thereof.
[0003]
Consumer product according to either claim 1 or 2, characterized by the fact that the polymeric shell comprises a polymeric material selected from the group consisting of polyacrylates, polyethylenes, polyamides, polystyrenes, polyisoprene, polycarbonates, polyesters, polyureas, polyurethanes , polyolefins, polysaccharides, epoxy resins, vinyl polymers, urea crosslinked with formaldehyde or gluteraldehyde, crosslinked melamine with formaldehyde, gelatin-polyphosphate coacervation products, optionally cross-linked with gluteraldehyde, gelatin-gum arabic, co-preservation products, fluids, arabic gum, fluids polyamines reacted with polyisocyanates, acrylate monomers polymerized by free radical polymerization, silk, wool, gelatin, cellulose, alginate, proteins, and combinations thereof.
[0004]
Consumer product according to any one of claims 1 to 3, characterized in that the polymeric shell comprises a polyacrylate.
[0005]
Consumer product according to any one of claims 1 to 4, characterized in that the particles of the first metal are nanoparticles; preferably wherein said nanoparticles have a particle size of less than 100 nm, for example, less than 50 nm, for example, 10 nm, for example, less than 5 nm, for example, less than 3 nm .
[0006]
Consumer product according to any one of claims 1 to 5, characterized by the fact that the first metal is palladium, platinum, silver, gold, copper, nickel, tin or a combination thereof; and where the second metal is silver, gold, nickel, copper or a combination thereof.
[0007]
Consumer product according to any one of claims 1 to 6, characterized in that the density of said particles in the polymeric shell is such that said particles cover from 0.1 to 80% of the surface area of the polymeric shell.
[0008]
Consumer product according to any one of claims 1 to 7, characterized by the fact that: (i) the first metal is platinum and the second metal is gold; (ii) the first metal is gold and the second metal is silver; or (iii) the first metal is gold and the second metal is copper.
[0009]
Consumer product according to any one of claims 1 to 8, characterized in that the metallic coating has a maximum thickness of 500 nm, for example, a maximum thickness of 300 nm, for example, a maximum thickness of 150 nm , for example, a maximum thickness of 100 nm, for example, a maximum thickness of 50 nm; preferably where the metallic coating has a minimum thickness of 1 nm.
[0010]
Consumer product according to any one of claims 1 to 9, characterized in that the coated microcapsule has a particle size of 0.1 micron to 500 micron.
[0011]
Consumer product according to any one of claims 1 to 10, characterized in that said adjunct ingredient comprises a mixture of materials, said mixture comprising: i) from 50% to 99.9% by weight of the composition, of ethanol; and ii) from 0.5% to 50% of a fragrance.
[0012]
Consumer product according to any one of claims 1 to 11, characterized by the fact that it is selected from the group consisting of hair care products, deodorants and antiperspirants, personal cleansing, colored cosmetics, skin treatment methods, products referring to orally administered materials to enhance the appearance of hair, skin, and / or nails, shaving product, body spray, fine fragrance products, fabric care products, hard surfaces and any other surfaces in the fabric and home care area, products referring to disposable absorbent and / or non-absorbent articles, hand soaps, shampoos, oral care utensils, clothing and products refer to catamenial pads, incontinence pads, interlabial pads, panties liners, pessaries, sanitary wipes, tampons and buffer applicators, and / or wipes; Preferably, the product is an oral care composition; more preferably the product is selected from the group consisting of products intended to treat and / or clean hair, styler; deodorants and antiperspirants, personal cleaning products, cosmetics products; products related to skin treatment, shaving product, bleaching / coloring products, body spray and fine fragrances.

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法律状态:
2018-02-14| B25A| Requested transfer of rights approved|Owner name: NOXELL CORPORATION (US) |

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-02-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-04-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201462092577P| true| 2014-12-16|2014-12-16|

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US62/092,577|2014-12-16|

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